JP4473103B2 - Negative resist material and pattern forming method using the same - Google Patents

Description

  The present invention is sensitive to high energy rays such as ultraviolet rays, far ultraviolet rays, electron beams, soft X rays, X rays, excimer lasers, γ rays, synchrotron radiation, etc. The present invention relates to a resist material suitable as a pattern forming material.

In recent years, along with higher integration and higher speed of LSI, pattern rule miniaturization is progressing rapidly. The background of rapid progress in miniaturization includes an increase in the NA of the projection lens, an improvement in resist performance, and a shorter wavelength of exposure light. In particular, the shortening of the wavelength from i-line (365 nm) to KrF (248 nm) has brought about a major change, and the mass production of 0.18 um rule devices has become possible.
For such high resist resolution and high sensitivity, acid-amplified chemically amplified positive resist materials (see, for example, Patent Documents 1 and 2) have excellent characteristics. In particular, it became a mainstream resist material.

  Resist materials for KrF excimer lasers are generally used in 0.3 micron processes, passed through the 0.25 micron rule, and are now applied to mass production of the 0.18 micron rule. Has also begun, and the momentum of miniaturization is increasingly accelerated. Furthermore, it is expected that the design rule will be reduced to 0.13 μm or less by shortening the wavelength from KrF (248 nm) to ArF (193 nm), but novolak and polyvinylphenol resins that have been used conventionally Has very strong absorption in the vicinity of 193 nm and cannot be used as a base resin for resist. Therefore, acrylic and cycloolefin-based alicyclic resins have been studied in order to ensure transparency and necessary dry etching resistance (see, for example, Patent Documents 3 and 4).

  In particular, a (meth) acrylic-based resin resist having high resolution has been studied. As a (meth) acrylic resin for a positive resist, a combination of (meth) acryl having a methyladamantane ester as an acid labile group unit and (meth) acryl having a lactone ring ester as an adhesive group unit has been proposed. (For example, see Patent Document 5). Furthermore, norbornyl lactone has been proposed as an adhesive group with enhanced etching resistance (see, for example, Patent Documents 6 and 7). However, in order to cope with the miniaturization of pattern rules, further improvement in adhesion has been demanded. There has also been a demand for improvement in alkali dissolution rate contrast before and after exposure.

  On the other hand, the negative resist material for ArF uses a crosslinking reaction between an alcohol and a carboxyl group or a crosslinking reaction between a crosslinking agent and an alcohol. However, these conventional resist materials use carboxyl groups as alkali-soluble groups, so that swelling in the developer occurs and the collapse of the limit pattern is conspicuous. Therefore, a reduction in swelling during development has been demanded.

JP-B-2-27660 JP 63-27829 A JP-A-9-73173 Japanese Patent Laid-Open No. 10-10739 JP-A-9-90637 JP 2000-26446 A JP 2000-159758 A

  The present invention has been made in view of such problems, and is a resist material that has high adhesion, and that the alkali dissolution rate contrast before and after exposure is significantly high, and has high sensitivity and high resolution. A further object of the present invention is to provide a resist material suitable for use as a fine pattern forming material for VLSI manufacturing or photomask pattern creation, in which pattern collapse and line edge roughness are reduced because swelling during development is small. .

（上記一般式（１）中、Ｒ^１は水素原子、または環・有橋環を有してもよい炭素数１〜２０の炭化水素基で、ヘテロ原子を含んでもよく、少なくともカルボキシル基、ヒドロキシ基、ラクトン環、エステル基、エーテル基のいずれか１以上を有する。） The present invention has been made in order to solve the above problems, and comprises a chemically amplified negative resist material characterized in that it contains at least a polymer compound having a repeating unit represented by the following general formula (1). you provide.

(In the above general formula (1), R ¹ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a ring or a bridged ring, may contain a hetero atom, and is at least a carboxyl group, a hydroxy group Any one or more of a group, a lactone ring, an ester group, and an ether group.)

  Such a chemically amplified negative resist material containing the polymer compound of the present invention as a base resin has high cross-linking efficiency, so the alkali dissolution rate contrast before and after exposure is significantly high, the adhesion is high, and the sensitivity is high. It has high resolution. In addition, swelling during development is small. Therefore, since it has these characteristics, it is highly practical and suitable as a material for forming a fine pattern for VLSI manufacturing or photomask pattern creation.

（上記一般式（２）中、Ｒ^２、Ｒ^３は水素原子、又はＲ^２とＲ^３が結合してメチレン基、エチレン基、−Ｏ−、−S−を形成していてもよく、Ｒ^４は単結合、炭素数１〜４のアルキレン基、全部又は一部の水素原子がフッ素原子で置換されたアルキレン基、Ｒ^５、Ｒ^６は水素原子、フッ素原子、炭素数１〜４のアルキル基、全部又は一部の水素原子がフッ素原子で置換されたアルキル基であり、少なくともＲ^５とＲ^６のいずれか一方に１個以上のフッ素原子を含む。ｎは１又は２である。） Further, the present invention is at least, that provides a resist material characterized in that those comprising a polymer compound having a repeating unit represented by the following general formula (2).

(In the general formula (2), R ² and R ³ may be a hydrogen atom, or R ² and R ³ may be bonded to form a methylene group, an ethylene group, —O—, —S—, ⁴ is a single bond, an alkylene group having 1 to 4 carbon atoms, an alkylene group in which all or a part of hydrogen atoms are substituted with fluorine atoms, R ⁵ and R ⁶ are hydrogen atoms, fluorine atoms, alkyl having 1 to 4 carbon atoms A group, an alkyl group in which all or some of the hydrogen atoms are substituted with fluorine atoms, and at least one of R ⁵ and R ⁶ contains one or more fluorine atoms, and n is 1 or 2.)

（上記一般式（３）中、Ｒ^２、Ｒ^３は水素原子、又はＲ^２とＲ^３が結合してメチレン基、エチレン基、−Ｏ−、−S−を形成していてもよく、Ｒ^４は単結合、炭素数１〜４のアルキレン基、全部又は一部の水素原子がフッ素原子で置換されたアルキレン基、Ｒ^５、Ｒ^６は水素原子、フッ素原子、炭素数１〜４のアルキル基、全部又は一部の水素原子がフッ素原子で置換されたアルキル基であり、少なくともＲ^５とＲ^６のいずれか一方に１個以上のフッ素原子を含む。Ｒ^７は水素原子、メチル基、―ＣＨ_２−Ｏ−Ｒ^１である。Ｒ^１は水素原子、または環・有橋環を有してもよい炭素数１〜２０の炭化水素基で、ヘテロ原子を含んでもよく、少なくともカルボキシル基、ヒドロキシ基、ラクトン環、エステル基、エーテル基のいずれか１以上を有する。Ｒ^８は水素原子、または環・有橋環を有してもよい炭素数１〜２０の炭化水素基で、ヘテロ原子を含んでもよく、少なくともカルボキシル基、ヒドロキシ基、ラクトン環、エステル基、エーテル基のいずれか１以上を有する。ａ、ｂは０＜ａ＜１、０＜ｂ＜１、０＜ａ＋ｂ≦１の範囲である。ｎは１又は２である。） Further, the present invention is at least, that provides a resist material characterized in that those comprising a polymer compound having a repeating unit represented by the following general formula (3).

(In the general formula (3), R ² and R ³ may be a hydrogen atom, or R ² and R ³ may be bonded to form a methylene group, an ethylene group, —O—, —S—, ⁴ is a single bond, an alkylene group having 1 to 4 carbon atoms, an alkylene group in which all or a part of hydrogen atoms are substituted with fluorine atoms, R ⁵ and R ⁶ are hydrogen atoms, fluorine atoms, alkyl having 1 to 4 carbon atoms Group, an alkyl group in which all or some of the hydrogen atoms are substituted with fluorine atoms, and at least one of R ⁵ and R ⁶ contains one or more fluorine atoms, R ⁷ is a hydrogen atom, a methyl group, —CH ₂ —O—R ^1. R ¹ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a ring or a bridged ring, may contain a hetero atom, and is at least a carboxyl group. , Hydroxy group, lactone ring, ester group, ether group In .R ⁸ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a ring-bridged, which has the above, and may contain a hetero atom, at least a carboxyl group, hydroxy group, a lactone ring, (It has one or more of an ester group and an ether group. A and b are in the range of 0 <a <1, 0 <b <1, 0 <a + b ≦ 1, and n is 1 or 2.)

（上記一般式（４）中、Ｒ^１は水素原子、または環・有橋環を有してもよい炭素数１〜２０の炭化水素基で、ヘテロ原子を含んでもよく、少なくともカルボキシル基、ヒドロキシ基、ラクトン環、エステル基、エーテル基のいずれか１以上を有する。Ｒ^４は単結合、炭素数１〜４のアルキレン基、全部又は一部の水素原子がフッ素原子で置換されたアルキレン基のいずれかである。Ｒ^９は水素原子またはメチル基である。Ｒ^１０は炭素数１〜１２の直鎖状・分岐状・環状・有橋環式のいずれかの炭化水素基であり、全部又は一部の水素原子がフッ素原子で置換されていても良く、ヒドロキシ基、エーテル基、ラクトン環、−Ｏ−、−S−のいずれか１以上を有していても良い。Ｒ^１１、Ｒ^１２はそれぞれ独立に水素原子、フッ素原子、炭素数１〜４のアルキル基、全部又は一部の水素原子がフッ素原子で置換されたアルキル基で、少なくともＲ^１１とＲ^１２のいずれか一方に１個以上のフッ素原子を含む。また、Ｒ^１１とＲ^１２のいずれか一方がＲ^１０と接続して環を形成していても良い。Ｒ^１６は単結合または炭素数１〜４のアルキレン基である。ｃ、ｄは０＜ｃ＜１、０＜ｄ＜１、０＜ｃ＋ｄ≦１の範囲である。ｎは１又は２である。） Moreover, this invention provides the resist material characterized by including the high molecular compound which has a repeating unit shown by following General formula (4) at least.

(In the general formula (4), R ¹ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a ring or a bridged ring, may contain a hetero atom, and is at least a carboxyl group, a hydroxy group Any one or more of a group, a lactone ring, an ester group, and an ether group, R ⁴ is a single bond, an alkylene group having 1 to 4 carbon atoms, or an alkylene group in which all or some of the hydrogen atoms are substituted with fluorine atoms. R ⁹ is a hydrogen atom or a methyl group, and R ¹⁰ is a linear, branched, cyclic or bridged hydrocarbon group having 1 to 12 carbon atoms, all or even if some of the hydrogen atoms are substituted with fluorine atoms may, hydroxy group, an ether group, a lactone ring, -O -, - which may have any one or more S- of .R ^11, R ¹² Are independently hydrogen atom, fluorine atom, charcoal C1-4 alkyl group, all or part of an alkyl group wherein a hydrogen atom has been substituted with a fluorine atom, including at least R ¹¹ and one or more fluorine atoms either one of R ^12. In addition, R Any one of ¹¹ and R ¹² may be connected to R ¹⁰ to form a ring, R ¹⁶ is a single bond or an alkylene group having 1 to 4 carbon atoms, and c and d are 0 <c <1. 0 <d <1, 0 <c + d ≦ 1, n is 1 or 2.)

（上記一般式（５）中、Ｒ^１は水素原子、または環・有橋環を有してもよい炭素数１〜２０の炭化水素基で、ヘテロ原子を含んでもよく、少なくともカルボキシル基、ヒドロキシ基、ラクトン環、エステル基、エーテル基のいずれか１以上を有する。Ｒ^４は単結合、炭素数１〜４のアルキレン基、全部又は一部の水素原子がフッ素原子で置換されたアルキレン基、Ｒ^５、Ｒ^６は水素原子、フッ素原子、炭素数１〜４のアルキル基、全部又は一部の水素原子がフッ素原子で置換されたアルキル基であり、少なくともＲ^５とＲ^６のいずれか一方に１個以上のフッ素原子を含む。Ｒ^９は水素原子またはメチル基である。Ｄ^１、Ｅ^１、Ｆ^１はそれぞれ炭素数３〜１２の環状炭化水素基または有橋環式炭化水素基であり、ヒドロキシ基、−Ｏ−、−S−を含んでいてもよい。Ｒ^１３、Ｒ^１４、Ｒ^１５はそれぞれ独立に水素原子、フッ素原子、トリフルオロメチル基のいずれかであり、少なくともＲ^１３〜Ｒ^１５のいずれかが１個以上のフッ素原子を含む。Ｒ^１６は単結合または炭素数１〜４のアルキレン基、Ｒ^１７は水素原子またはメチル基である。ｃ、ｄ−１、ｄ−２、ｄ−３は、０＜ｃ＜１、０≦（ｄ−１）＜１、０≦（ｄ−２）＜１、０≦（ｄ−３）＜１、０＜（ｄ−１）＋（ｄ−２）＋（ｄ−３）＜１の範囲である。ｎは１又は２である。） Further, the present invention is at least, that provides a resist material characterized in that those comprising a polymer compound having a repeating unit represented by the following general formula (5).

(In the above general formula (5), R ¹ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a ring or a bridged ring, may contain a hetero atom, and is at least a carboxyl group, a hydroxy group Any one or more of a group, a lactone ring, an ester group, and an ether group, R ⁴ is a single bond, an alkylene group having 1 to 4 carbon atoms, an alkylene group in which all or part of hydrogen atoms are substituted with fluorine atoms, R ⁵ and R ⁶ are a hydrogen atom, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an alkyl group in which all or part of the hydrogen atoms are substituted with fluorine atoms, and at least one of R ⁵ and R ⁶ And R ⁹ is a hydrogen atom or a methyl group, and D ¹ , E ¹ and F ¹ are each a cyclic hydrocarbon group or a bridged cyclic hydrocarbon group having 3 to 12 carbon atoms. Yes, hydroxy group, -O- R ¹³ , R ¹⁴ , and R ¹⁵ are each independently a hydrogen atom, a fluorine atom, or a trifluoromethyl group, and at least one of R ^{13 to} R ¹⁵ is 1 R ¹⁶ is a single bond or an alkylene group having 1 to 4 carbon atoms, R ¹⁷ is a hydrogen atom or a methyl group, c, d-1, d-2, d-3 are 0 <C <1, 0 ≦ (d−1) <1, 0 ≦ (d−2) <1, 0 ≦ (d−3) <1, 0 <(d−1) + (d−2) + ( d-3) <1 range, n is 1 or 2)

  The resist material of the present invention containing the polymer compound represented by the general formulas (2) to (5) as a base resin has a sufficiently small swelling during development, so that pattern collapse and line edge roughness are further reduced. The crosslinking efficiency is high, the alkali dissolution rate contrast before and after exposure is significantly high, the adhesion is high, and the sensitivity is high and the resolution is high. Therefore, since it has these characteristics, it is more suitable as a fine pattern forming material for VLSI manufacturing or photomask pattern creation.

Further, the present invention, the a resist material, that provides a resist material which is a chemically amplified resist material containing at least an organic solvent and an acid generator.

  Thus, by containing an acid generator and utilizing an acid catalyzed reaction, it is possible to obtain an extremely sensitive resist material, which is extremely useful as a highly sensitive resist required in recent years.

At this time, the resist material of the present invention, have the preferred to the chemically amplified negative resist composition further contains a crosslinking agent.

  Thus, by further blending a crosslinking agent with the resist material of the present invention, the polymer compound is crosslinked in the exposed area, the molecular weight is increased, and the dissolution rate in the developer can be surely lowered.

Further, in the resist material of the present invention, Ru can be a basic compound as a further additive.

  By adding the basic compound in this manner, for example, the acid diffusion rate in the resist film can be suppressed and the resolution can be improved.

Such a resist material of the present invention comprises at least a step of applying the resist material on a substrate, a step of exposing to a high energy beam or an electron beam after heat treatment, and a step of developing using a developer. by performing, Ru can be used as a method for forming a pattern on a semiconductor substrate or a mask substrate.

  Needless to say, development may be performed after the post-exposure heat treatment, and various other processes such as an etching process, a resist removal process, and a cleaning process may be performed.

  As described above, according to the present invention, the crosslinking efficiency is high, the alkali dissolution rate contrast before and after exposure is significantly high, the adhesiveness is high, and further, the swelling during development is small, so the sensitivity is high. It is possible to obtain a resist material that has high resolution and low line edge roughness, and that is particularly suitable as a fine pattern forming material for VLSI manufacturing or photomask pattern creation.

Hereinafter, although embodiment of this invention is described, this invention is not limited to these.
Along with the recent high integration and high speed of LSI, high sensitivity and high resolution in exposure with high energy rays, and since swelling during development is suppressed, line edge roughness is small. There is a demand for a resist material suitable as a fine pattern forming material for VLSI manufacturing or photomask pattern creation.

  In response to such demands, for example, Polym. Mater. Sci. Eng. 1997, 77, p449-450 is used as a resist material in which line edge roughness is reduced by suppressing swelling during development. A resist material having a functional group has been proposed. Hexafluoroalcohol is said to have the same degree of acidity as phenol, and has moderate solubility in an alkaline developer, so that swelling during development hardly occurs. Also, SPIE vol. 5039 (2003) In p61, a high-performance cycloolefin polymer-based resist material having hexafluoroalcohol as an adhesive group has been reported. Furthermore, SPIE vol. In 3999 p62, a negative resist material having hexafluoroalcohol as an adhesive group has been proposed, and reduction of pattern collapse due to swelling has been reported.

  Moreover, as resists that improve adhesion, for example, JP-A-6-27665 and JP-A-2002-244292 propose plating resist materials and color filter resist materials obtained by copolymerizing an α-hydroxymethylacrylic acid derivative. It has been reported that the α-hydroxymethylacryl group improves plating resistance and improves adhesion. Also, SPIE Vol. 5039 (2003) p682 proposes an acrylic monomer having an α-hydroxymethyl group.

  Based on these findings, the present inventors have intensively studied to solve the above problems. As a result, the present inventors paid attention to the high reactivity and high crosslinking efficiency because the hydroxy group of α-hydroxymethyl acrylate is primary. That is, a chemically amplified negative resist material copolymerized with an α-hydroxymethylacrylic acid derivative, or an acrylate having an adhesive group with an alcohol substituted with a fluoroalkyl group at the α-position, such as hexafluoroalcohol, and α-hydroxymethyl For resist materials copolymerized with acrylate, or resist materials containing an acrylate having an alcohol substituted with a fluoroalkyl group at the α-position, such as α-hydroxymethyl and hexafluoroalcohol, before and after exposure High alkali dissolution contrast, high adhesion, high sensitivity and high resolution, low line edge roughness due to swelling during development, high adhesion, especially for VLSI manufacturing or photomask patterns Suitable as a material for forming fine patterns in production The present inventors have found that the resist material can be used and completed the present invention.

（上記一般式（１）中、Ｒ^１は水素原子、または環・有橋環を有してもよい炭素数１〜２０の炭化水素基で、ヘテロ原子を含んでもよく、少なくともカルボキシル基、ヒドロキシ基、ラクトン環、エステル基、エーテル基のいずれか１以上を有する。） That is, the resist material according to the present invention is a chemically amplified negative resist material characterized in that it contains at least a polymer compound having a repeating unit represented by the following general formula (1).

(In the above general formula (1), R ¹ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a ring or a bridged ring, may contain a hetero atom, and is at least a carboxyl group, a hydroxy group Any one or more of a group, a lactone ring, an ester group, and an ether group.)

That is, the hydrocarbon group represented by R ^{1 in} the above formula is an adhesive group having a hydrophilic group such as a carboxyl group, a hydroxy group, a lactone ring, an ester group, or an ether group.
In such chemically amplified negative resist materials containing α-hydroxymethyl acrylate as a base resin, the hydroxy group of α-hydroxymethyl acrylate is primary and highly reactive, and has high crosslinking efficiency. The alkali dissolution rate contrast before and after exposure is significantly increased. Furthermore, the adhesion is improved by the α-hydroxymethylacryl group. In addition, swelling during development is small. Therefore, the chemically amplified negative resist material of the present invention having such characteristics can be a highly sensitive resist material, and is particularly suitable as a fine pattern forming material and a mask pattern forming material for VLSI manufacturing. It is.
The chemically amplified negative resist material according to the present invention contains one or more repeating units represented by the general formula (1) having different R ¹ .

（上記一般式（２）中、Ｒ^２、Ｒ^３は水素原子、又はＲ^２とＲ^３が結合してメチレン基、エチレン基、−Ｏ−、−S−を形成していてもよく、Ｒ^４は単結合、炭素数１〜４のアルキレン基、全部又は一部の水素原子がフッ素原子で置換されたアルキレン基、Ｒ^５、Ｒ^６は水素原子、フッ素原子、炭素数１〜４のアルキル基、全部又は一部の水素原子がフッ素原子で置換されたアルキル基であり、少なくともＲ^５とＲ^６のいずれか一方に１個以上のフッ素原子を含む。ｎは１又は２である。） The resist material according to the present invention is a resist material characterized in that it contains at least a polymer compound having a repeating unit represented by the following general formula (2).

(In the general formula (2), R ² and R ³ may be a hydrogen atom, or R ² and R ³ may be bonded to form a methylene group, an ethylene group, —O—, —S—, ⁴ is a single bond, an alkylene group having 1 to 4 carbon atoms, an alkylene group in which all or a part of hydrogen atoms are substituted with fluorine atoms, R ⁵ and R ⁶ are hydrogen atoms, fluorine atoms, alkyl having 1 to 4 carbon atoms A group, an alkyl group in which all or some of the hydrogen atoms are substituted with fluorine atoms, and at least one of R ⁵ and R ⁶ contains one or more fluorine atoms, and n is 1 or 2.)

（上記一般式（３）中、Ｒ^２、Ｒ^３は水素原子、又はＲ^２とＲ^３が結合してメチレン基、エチレン基、−Ｏ−、−S−を形成していてもよく、Ｒ^４は単結合、炭素数１〜４のアルキレン基、全部又は一部の水素原子がフッ素原子で置換されたアルキレン基、Ｒ^５、Ｒ^６は水素原子、フッ素原子、炭素数１〜４のアルキル基、全部又は一部の水素原子がフッ素原子で置換されたアルキル基であり、少なくともＲ^５とＲ^６のいずれか一方に１個以上のフッ素原子を含む。Ｒ^７は水素原子、メチル基、―ＣＨ_２−Ｏ−Ｒ^１である。Ｒ^１は水素原子、または環・有橋環を有してもよい炭素数１〜２０の炭化水素基で、ヘテロ原子を含んでもよく、少なくともカルボキシル基、ヒドロキシ基、ラクトン環、エステル基、エーテル基のいずれか１以上を有する。Ｒ^８は水素原子、または環・有橋環を有してもよい炭素数１〜２０の炭化水素基で、ヘテロ原子を含んでもよく、少なくともカルボキシル基、ヒドロキシ基、ラクトン環、エステル基、エーテル基のいずれか１以上を有する。ａ、ｂは０＜ａ＜１、０＜ｂ＜１、０＜ａ＋ｂ≦１の範囲である。ｎは１又は２である。） Further, as represented by the following general formula (3), in addition to the repeating unit represented by the general formula (2), a repeating unit b may be included.

(In the general formula (3), R ² and R ³ may be a hydrogen atom, or R ² and R ³ may be bonded to form a methylene group, an ethylene group, —O—, —S—, ⁴ is a single bond, an alkylene group having 1 to 4 carbon atoms, an alkylene group in which all or a part of hydrogen atoms are substituted with fluorine atoms, R ⁵ and R ⁶ are hydrogen atoms, fluorine atoms, alkyl having 1 to 4 carbon atoms Group, an alkyl group in which all or some of the hydrogen atoms are substituted with fluorine atoms, and at least one of R ⁵ and R ⁶ contains one or more fluorine atoms, R ⁷ is a hydrogen atom, a methyl group, —CH ₂ —O—R ^1. R ¹ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a ring or a bridged ring, may contain a hetero atom, and is at least a carboxyl group. , Hydroxy group, lactone ring, ester group, ether group In .R ⁸ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a ring-bridged, which has the above, and may contain a hetero atom, at least a carboxyl group, hydroxy group, a lactone ring, (It has one or more of an ester group and an ether group. A and b are in the range of 0 <a <1, 0 <b <1, 0 <a + b ≦ 1, and n is 1 or 2.)

（上記一般式（４）中、Ｒ^１は水素原子、または環・有橋環を有してもよい炭素数１〜２０の炭化水素基で、ヘテロ原子を含んでもよく、少なくともカルボキシル基、ヒドロキシ基、ラクトン環、エステル基、エーテル基のいずれか１以上を有する。Ｒ^４は単結合、炭素数１〜４のアルキレン基、全部又は一部の水素原子がフッ素原子で置換されたアルキレン基のいずれかである。Ｒ^９は水素原子またはメチル基である。Ｒ^１０は炭素数１〜１２の直鎖状・分岐状・環状・有橋環式のいずれかの炭化水素基であり、全部又は一部の水素原子がフッ素原子で置換されていても良く、ヒドロキシ基、エーテル基、ラクトン環、−Ｏ−、−S−のいずれか１以上を有していても良い。Ｒ^１１、Ｒ^１２はそれぞれ独立に水素原子、フッ素原子、炭素数１〜４のアルキル基、全部又は一部の水素原子がフッ素原子で置換されたアルキル基で、少なくともＲ^１１とＲ^１２のいずれか一方に１個以上のフッ素原子を含む。また、Ｒ^１１とＲ^１２のいずれか一方がＲ^１０と接続して環を形成していても良い。Ｒ^１６は単結合または炭素数１〜４のアルキレン基である。ｃ、ｄは０＜ｃ＜１、０＜ｄ＜１、０＜ｃ＋ｄ≦１の範囲である。ｎは１又は２である。） Further, as represented by the following general formula (4), a repeating unit d may be included in addition to the repeating unit represented by the general formula (1).

(In the general formula (4), R ¹ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a ring or a bridged ring, may contain a hetero atom, and is at least a carboxyl group, a hydroxy group Any one or more of a group, a lactone ring, an ester group, and an ether group, R ⁴ is a single bond, an alkylene group having 1 to 4 carbon atoms, or an alkylene group in which all or some of the hydrogen atoms are substituted with fluorine atoms. R ⁹ is a hydrogen atom or a methyl group, and R ¹⁰ is a linear, branched, cyclic or bridged hydrocarbon group having 1 to 12 carbon atoms, all or even if some of the hydrogen atoms are substituted with fluorine atoms may, hydroxy group, an ether group, a lactone ring, -O -, - which may have any one or more S- of .R ^11, R ¹² Are independently hydrogen atom, fluorine atom, charcoal C1-4 alkyl group, all or part of an alkyl group wherein a hydrogen atom has been substituted with a fluorine atom, including at least R ¹¹ and one or more fluorine atoms either one of R ^12. In addition, R Any one of ¹¹ and R ¹² may be connected to R ¹⁰ to form a ring, R ¹⁶ is a single bond or an alkylene group having 1 to 4 carbon atoms, and c and d are 0 <c <1. 0 <d <1, 0 <c + d ≦ 1, n is 1 or 2.)

（上記一般式（５）中、Ｒ^１は水素原子、または環・有橋環を有してもよい炭素数１〜２０の炭化水素基で、ヘテロ原子を含んでもよく、少なくともカルボキシル基、ヒドロキシ基、ラクトン環、エステル基、エーテル基のいずれか１以上を有する。Ｒ^４は単結合、炭素数１〜４のアルキレン基、全部又は一部の水素原子がフッ素原子で置換されたアルキレン基、Ｒ^５、Ｒ^６は水素原子、フッ素原子、炭素数１〜４のアルキル基、全部又は一部の水素原子がフッ素原子で置換されたアルキル基であり、少なくともＲ^５とＲ^６のいずれか一方に１個以上のフッ素原子を含む。Ｒ^９は水素原子またはメチル基である。Ｄ^１、Ｅ^１、Ｆ^１はそれぞれ炭素数３〜１２の環状炭化水素基または有橋環式炭化水素基であり、ヒドロキシ基、−Ｏ−、−S−を含んでいてもよい。Ｒ^１３、Ｒ^１４、Ｒ^１５はそれぞれ独立に水素原子、フッ素原子、トリフルオロメチル基のいずれかであり、少なくともＲ^１３〜Ｒ^１５のいずれかが１個以上のフッ素原子を含む。Ｒ^１６は単結合または炭素数１〜４のアルキレン基、Ｒ^１７は水素原子またはメチル基である。ｃ、ｄ−１、ｄ−２、ｄ−３は、０＜ｃ＜１、０≦（ｄ−１）＜１、０≦（ｄ−２）＜１、０≦（ｄ−３）＜１、０＜（ｄ−１）＋（ｄ−２）＋（ｄ−３）＜１の範囲である。ｎは１又は２である。） In this case, the repeating unit d in the general formula (4) may be the repeating units d-1, d-2, and d-3 in the following general formula (5).

(In the above general formula (5), R ¹ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a ring or a bridged ring, may contain a hetero atom, and is at least a carboxyl group, a hydroxy group Any one or more of a group, a lactone ring, an ester group, and an ether group, R ⁴ is a single bond, an alkylene group having 1 to 4 carbon atoms, an alkylene group in which all or part of hydrogen atoms are substituted with fluorine atoms, R ⁵ and R ⁶ are a hydrogen atom, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an alkyl group in which all or part of the hydrogen atoms are substituted with fluorine atoms, and at least one of R ⁵ and R ⁶ And R ⁹ is a hydrogen atom or a methyl group, and D ¹ , E ¹ and F ¹ are each a cyclic hydrocarbon group or a bridged cyclic hydrocarbon group having 3 to 12 carbon atoms. Yes, hydroxy group, -O- R ¹³ , R ¹⁴ , and R ¹⁵ are each independently a hydrogen atom, a fluorine atom, or a trifluoromethyl group, and at least one of R ^{13 to} R ¹⁵ is 1 R ¹⁶ is a single bond or an alkylene group having 1 to 4 carbon atoms, R ¹⁷ is a hydrogen atom or a methyl group, c, d-1, d-2, d-3 are 0 <C <1, 0 ≦ (d−1) <1, 0 ≦ (d−2) <1, 0 ≦ (d−3) <1, 0 <(d−1) + (d−2) + ( d-3) <1 range, n is 1 or 2)

Thus, copolymerization of an acrylate having an adhesive group with an alcohol substituted at the α-position with a fluoroalkyl group or the like and an α-hydroxymethyl acrylate derivative, or α-hydroxymethyl and α-position substituted with a fluoroalkyl group or the like If the resist material contains an acrylate derivative having alcohol in one molecule, the hydroxy group of the α-hydroxymethyl group is primary and highly reactive, and the crosslinking efficiency is high. Dissolution rate contrast is significantly increased. Moreover, adhesiveness improves by having (alpha) hydroxymethyl group. Further, the alcohol substituted at the α-position with a fluoroalkyl group or the like suppresses swelling during development, and pattern collapse and line edge roughness are reduced. A resist material having such characteristics is particularly suitable as a fine pattern forming material and a mask pattern forming material for VLSI manufacturing.
In the general formula (3), the ratio of the repeating units a and b is in the range of 0.1 ≦ a / (a + b) ≦ 0.8 and 0.2 ≦ b / (a + b) ≦ 0.9. Is more preferable.
In the general formula (4), the ratio between the repeating units c and d is in the range of 0.2 ≦ c / (c + d) ≦ 0.9 and 0.1 ≦ d / (c + d) ≦ 0.8. Is more preferable.
Moreover, in the said General formula (5), the ratio of the repeating unit c and d-1, d-2, d-3 is 0.2 <= c / (c + (d-1) + (d-2) + (d −3)) ≦ 0.9, 0.1 ≦ (d−1) + (d−2) + (d−3) / (c + (d−1) + (d−2) + (d−3) ) ≦ 0.8 is more preferable.
The resist material according to the present invention contains one or more repeating units c having different R ¹ in the case of the general formulas (4) and (5).

The polymerizable monomers necessary for obtaining the polymer compound according to the present invention as described above are exemplified below.
The polymerizable monomer of α-hydroxymethylacrylic acid for obtaining the repeating unit of the general formula (1) and the repeating unit c in the general formulas (4) and (5) is, for example, an acrylate ester and formaldehyde of a tertiary amine. It can be obtained by reacting in the presence.

Specific examples of such a polymerizable monomer of α-hydroxymethylacrylic acid are given below.

Moreover, the polymerizable monomer for obtaining the repeating unit in General formula (2) and the repeating unit a in General formula (3) can be illustrated below.

Moreover, the polymerizable monomer for obtaining the repeating unit b in General formula (3) can be illustrated below, for example.

Moreover, the polymerizable compound for obtaining the repeating unit d-1 in General formula (5) can illustrate the following compound, for example.

Moreover, the polymerizable compound for obtaining the repeating unit d-2 in General formula (5) can illustrate the following compound, for example.

Moreover, the polymerizable compound for obtaining the repeating unit d-3 in General formula (5) can illustrate the following compound, for example.

（式中、Ｒ^２４、Ｒ^３９はそれぞれ水素原子、炭素数１〜４のアルキル基、ヒドロキシ基を有するアルキル基、ヒドロキシ基のいずれかである。Ｒ^４０は水素原子又はメチル基である。） The polymer compound of the resist material according to the present invention has the repeating units shown in the above general formulas (1) to (5), but may have other repeating units. Specifically, it may have a norbornene derivative, maleic anhydride, itaconic anhydride, acrylonitrile, (meth) acrylic acid derivative, vinyl ether derivative and the like which can be shown below.

(In the formula, R ²⁴ and R ³⁹ are each a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkyl group having a hydroxy group, or a hydroxy group. R ⁴⁰ is a hydrogen atom or a methyl group.)

The polymer compound of the present invention preferably has a mass average molecular weight (measurement method as described later) of 1,000 to 500,000, more preferably 2,000 to 30,000. preferable.
When the mass average molecular weight is large, the resist material is excellent in heat resistance. When the mass average molecular weight is small, the alkali solubility is improved, and the trailing phenomenon tends to hardly occur after pattern formation.

  Furthermore, in the polymer compound contained in the resist material of the present invention, when the molecular weight distribution (Mw / Mn) of the copolymer having a repeating unit represented by any one of the general formulas (1) to (5) is narrow There is no large difference in the molecular weight of the polymer, and it is difficult for foreign matter to be seen on the pattern after exposure or for the shape of the pattern to deteriorate. Since the influence of such molecular weight and molecular weight distribution tends to increase as the pattern rule becomes finer, the molecular weight distribution of the multi-component copolymer to be used is to obtain a resist material suitably used for fine pattern dimensions. A narrow dispersion of 1.0 to 2.0, particularly 1.0 to 1.5 is preferable. It is also possible to blend two or more polymers having different composition ratios, molecular weight distributions, and molecular weights.

  The resist material according to the present invention includes a polymer compound having a repeating unit represented by any one of the general formulas (1) to (5), but is further added to improve adhesion, dry etching resistance, and transparency. It is also possible to add other components. For example, (meth) acryl derivatives, styrene derivatives, hydroxystyrene derivatives, indene, benzofuran, indole, benzothiophene, methylene indan, acenaphthene derivatives, vinyl naphthalene derivatives, vinyl anthracene derivatives, vinyl acetate, (meth) acrylonitrile, vinyl pyrrolidone, etc. Can be mentioned.

  A method for synthesizing such a polymer compound according to the present invention is not particularly limited. For example, in an organic solvent, a monomer for obtaining the repeating unit in the above-described general formulas (1) to (5), or in addition A monomer copolymerizable with these can be present, and a radical initiator can be added to the monomer, followed by heat polymerization to be synthesized. Examples of the organic solvent used in the polymerization include toluene, benzene, tetrahydrofuran, diethyl ether, dioxane and the like. Moreover, as a polymerization initiator, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2-azobis (2-methylpropionate) Benzoyl peroxide, lauroyl peroxide, etc., and preferably polymerized by heating to 50 to 80 ° C. The reaction time is preferably 2 to 100 hours, more preferably 5 to 20 hours.

  The organic solvent that can be used in the resist material according to the present invention is not particularly limited as long as it dissolves a base resin, an acid generator, a crosslinking agent, and other additives. Specific examples thereof include ketones such as cyclohexanone and methyl-2-amyl ketone; 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol and the like. Alcohols: ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, lactic acid Ethyl, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate , Tert-butyl acetate, tert-butyl propionate, esters such as propylene glycol mono tert-butyl ether acetate, lactones such as γ-butyl lactone, etc., and one or more of these can be used in combination However, it is not limited to these.

  In the resist material of the present invention, among these organic solvents, diethylene glycol dimethyl ether, 1-ethoxy-2-propanol, propylene glycol monomethyl ether acetate, and a mixed solvent thereof, which have the highest solubility of the acid generator in the resist component, are included. Preferably used.

  The blending amount of the organic solvent is preferably 200 to 1,000 parts, particularly preferably 400 to 800 parts, with respect to 100 parts of the base resin.

  In the resist material of the present invention, an acid generator for further promoting the crosslinking reaction by heat or the like can be added. There are acid generators that generate an acid by thermal decomposition and those that generate an acid by light irradiation, and any of them can be added.

As an acid generator used in the resist material of the present invention,
i. An onium salt of the following general formula (P1a-1), (P1a-2) or (P1b),
ii. A diazomethane derivative of the following general formula (P2):
iii. A glyoxime derivative of the following general formula (P3):
iv. A bissulfone derivative of the following general formula (P4):
v. A sulfonic acid ester of an N-hydroxyimide compound of the following general formula (P5),
vi. β-ketosulfonic acid derivatives,
vii. Disulfone derivatives,
viii. Nitrobenzyl sulfonate derivatives,
ix. Examples thereof include sulfonic acid ester derivatives.

（式中、Ｒ^101a、Ｒ^101b、Ｒ^101cはそれぞれ炭素数１〜１２の直鎖状、分岐状、環状のアルキル基、アルケニル基、オキソアルキル基、オキソアルケニル基、又は炭素数６〜２０のアリール基、炭素数７〜１２のアラルキル基又はアリールオキソアルキル基、を示し、これらの基の水素原子の一部又は全部がアルコキシ基等によって置換されていてもよい。また、Ｒ^101bとＲ^101cとは環を形成してもよく、環を形成する場合には、Ｒ^101b、Ｒ^101cはそれぞれ炭素数１〜６のアルキレン基を示す。Ｋ^-は非求核性対向イオンを表す。）

(In the formula, R ^101a , R ^101b and R ^101c are each a linear, branched or cyclic alkyl group, alkenyl group, oxoalkyl group, oxoalkenyl group having 6 to 20 carbon atoms, or 6 to 20 carbon atoms. An aryl group, an aralkyl group having 7 to 12 carbon atoms, or an aryloxoalkyl group, and a part or all of hydrogen atoms of these groups may be substituted by an alkoxy group, etc. R ^101b and R ^101c And may form a ring, and in the case of forming a ring, R ^101b and R ^101c each represent an alkylene group having 1 to 6 carbon atoms, and K ⁻ represents a non-nucleophilic counter ion.)

R ^101a , R ^101b and R ^101c may be the same as or different from each other. Specifically, as an alkyl group, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl Group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclopropylmethyl group, 4-methylcyclohexyl group, cyclohexylmethyl group, norbornyl group, adamantyl group, etc. Is mentioned. Examples of the alkenyl group include a vinyl group, an allyl group, a propenyl group, a butenyl group, a hexenyl group, and a cyclohexenyl group. Examples of the oxoalkyl group include 2-oxocyclopentyl group, 2-oxocyclohexyl group, and the like. 2-oxopropyl group, 2-cyclopentyl-2-oxoethyl group, 2-cyclohexyl-2-oxoethyl group, 2- (4 -Methylcyclohexyl) -2-oxoethyl group and the like can be mentioned. Examples of the oxoalkenyl group include 2-oxo-4-cyclohexenyl group and 2-oxo-4-propenyl group. Examples of the aryl group include a phenyl group, a naphthyl group, a p-methoxyphenyl group, an m-methoxyphenyl group, an o-methoxyphenyl group, an ethoxyphenyl group, a p-tert-butoxyphenyl group, and an m-tert-butoxyphenyl group. Alkylphenyl groups such as alkoxyphenyl groups, 2-methylphenyl groups, 3-methylphenyl groups, 4-methylphenyl groups, ethylphenyl groups, 4-tert-butylphenyl groups, 4-butylphenyl groups, dimethylphenyl groups, etc. Alkyl naphthyl groups such as methyl naphthyl group and ethyl naphthyl group, alkoxy naphthyl groups such as methoxy naphthyl group and ethoxy naphthyl group, dialkyl naphthyl groups such as dimethyl naphthyl group and diethyl naphthyl group, dimethoxy naphthyl group and diethoxy naphthyl group Dialkoxynaphthyl group And the like. Examples of the aralkyl group include a benzyl group, a phenylethyl group, and a phenethyl group. As the aryloxoalkyl group, 2-aryl-2-oxoethyl group such as 2-phenyl-2-oxoethyl group, 2- (1-naphthyl) -2-oxoethyl group, 2- (2-naphthyl) -2-oxoethyl group and the like Groups and the like. Non-nucleophilic counter ions of K ⁻ include halide ions such as chloride ions and bromide ions, triflate, fluoroalkyl sulfonates such as 1,1,1-trifluoroethanesulfonate, nonafluorobutanesulfonate, tosylate, and benzenesulfonate. And aryl sulfonates such as 4-fluorobenzene sulfonate and 1,2,3,4,5-pentafluorobenzene sulfonate, and alkyl sulfonates such as mesylate and butane sulfonate.

（式中、Ｒ^102a、Ｒ^102bはそれぞれ炭素数１〜８の直鎖状、分岐状、環状のアルキル基を示す。Ｒ¹⁰³は炭素数１〜１０の直鎖状、分岐状、環状のアルキレン基を示す。Ｒ^104a、Ｒ^104bはそれぞれ炭素数３〜７の２−オキソアルキル基を示す。Ｋ^-は非求核性対向イオンを表す。）

(Wherein R ^102a and R ^102b each represent a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. R ¹⁰³ is a linear, branched or cyclic alkylene having 1 to 10 carbon atoms. R ^104a and R ^104b each represent a 2-oxoalkyl group having 3 to 7 carbon atoms, and K ⁻ represents a non-nucleophilic counter ion.)

Specific examples of R ^102a and R ^102b include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. , Cyclopentyl group, cyclohexyl group, cyclopropylmethyl group, 4-methylcyclohexyl group, cyclohexylmethyl group and the like. R ¹⁰³ is methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, 1,4-cyclohexylene group, 1,2-cyclohexylene. Group, 1,3-cyclopentylene group, 1,4-cyclooctylene group, 1,4-cyclohexanedimethylene group and the like. ^{Examples of} R ^104a and R ^104b include a 2-oxopropyl group, a 2-oxocyclopentyl group, a 2-oxocyclohexyl group, and a 2-oxocycloheptyl group. Examples of K ⁻ are the same as those described in the formulas (P1a-1) and (P1a-2).

（式中、Ｒ¹⁰⁵、Ｒ¹⁰⁶は炭素数１〜１２の直鎖状、分岐状、環状のアルキル基又はハロゲン化アルキル基、炭素数６〜２０のアリール基又はハロゲン化アリール基、又は炭素数７〜１２のアラルキル基を示す。）

(Wherein R ¹⁰⁵ and R ¹⁰⁶ are linear, branched or cyclic alkyl groups or halogenated alkyl groups having 1 to 12 carbon atoms, aryl groups or halogenated aryl groups having 6 to 20 carbon atoms, or carbon numbers 7 to 12 aralkyl groups are shown.)

^Examples of the alkyl group of R ¹⁰⁵ and R ¹⁰⁶ include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, amyl Group, cyclopentyl group, cyclohexyl group, cycloheptyl group, norbornyl group, adamantyl group and the like. Examples of the halogenated alkyl group include a trifluoromethyl group, a 1,1,1-trifluoroethyl group, a 1,1,1-trichloroethyl group, and a nonafluorobutyl group. As the aryl group, an alkoxyphenyl group such as a phenyl group, p-methoxyphenyl group, m-methoxyphenyl group, o-methoxyphenyl group, ethoxyphenyl group, p-tert-butoxyphenyl group, m-tert-butoxyphenyl group, Examples thereof include alkylphenyl groups such as 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, ethylphenyl group, 4-tert-butylphenyl group, 4-butylphenyl group, and dimethylphenyl group. Examples of the halogenated aryl group include a fluorophenyl group, a chlorophenyl group, and 1,2,3,4,5-pentafluorophenyl group. Examples of the aralkyl group include a benzyl group and a phenethyl group.

（式中、Ｒ¹⁰⁷、Ｒ¹⁰⁸、Ｒ¹⁰⁹は炭素数１〜１２の直鎖状、分岐状、環状のアルキル基又はハロゲン化アルキル基、炭素数６〜２０のアリール基又はハロゲン化アリール基、又は炭素数７〜１２のアラルキル基を示す。Ｒ¹⁰⁸、Ｒ¹⁰⁹は互いに結合して環状構造を形成してもよく、環状構造を形成する場合、Ｒ¹⁰⁸、Ｒ¹⁰⁹はそれぞれ炭素数１〜６の直鎖状又は分岐状のアルキレン基を示す。Ｒ¹⁰⁵はＰ２式のものと同様である。）

(Wherein R ¹⁰⁷ , R ¹⁰⁸ , and R ¹⁰⁹ are linear, branched, or cyclic alkyl groups or halogenated alkyl groups having 1 to 12 carbon atoms, aryl groups or halogenated aryl groups having 6 to 20 carbon atoms, Or an aralkyl group having 7 to 12 carbon atoms, R ¹⁰⁸ and R ¹⁰⁹ may be bonded to each other to form a cyclic structure, and in the case of forming a cyclic structure, R ¹⁰⁸ and R ¹⁰⁹ each have 1 to 6 carbon atoms. And R ¹⁰⁵ is the same as that in formula P2.)

Examples of the alkyl group, halogenated alkyl group, aryl group, halogenated aryl group, and aralkyl group of R ¹⁰⁷ , R ¹⁰⁸ , and R ¹⁰⁹ include the same groups as those described for R ¹⁰⁵ and R ¹⁰⁶ . ^Examples of the alkylene group for R ¹⁰⁸ and R ¹⁰⁹ include a methylene group, an ethylene group, a propylene group, a butylene group, and a hexylene group.

（式中、Ｒ^101a、Ｒ^101bは前記と同様である。）

(In the formula, R ^101a and R ^101b are the same as described above.)

（式中、Ｒ¹¹⁰は炭素数６〜１０のアリーレン基、炭素数１〜６のアルキレン基又は炭素数２〜６のアルケニレン基を示し、これらの基の水素原子の一部又は全部は更に炭素数１〜４の直鎖状又は分岐状のアルキル基又はアルコキシ基、ニトロ基、アセチル基、又はフェニル基で置換されていてもよい。Ｒ¹¹¹は炭素数１〜８の直鎖状、分岐状又は置換のアルキル基、アルケニル基又はアルコキシアルキル基、フェニル基、又はナフチル基を示し、これらの基の水素原子の一部又は全部は更に炭素数１〜４のアルキル基又はアルコキシ基；炭素数１〜４のアルキル基、アルコキシ基、ニトロ基又はアセチル基で置換されていてもよいフェニル基；炭素数３〜５のヘテロ芳香族基；又は塩素原子、フッ素原子で置換されていてもよい。）

(In the formula, R ¹¹⁰ represents an arylene group having 6 to 10 carbon atoms, an alkylene group having 1 to 6 carbon atoms, or an alkenylene group having 2 to 6 carbon atoms, and some or all of the hydrogen atoms of these groups are further carbon atoms. It may be substituted with a linear or branched alkyl group or alkoxy group having 1 to 4 carbon atoms, a nitro group, an acetyl group, or a phenyl group, and R ¹¹¹ is a linear or branched chain having 1 to 8 carbon atoms. Or a substituted alkyl group, an alkenyl group or an alkoxyalkyl group, a phenyl group, or a naphthyl group, and part or all of the hydrogen atoms of these groups are further an alkyl group or alkoxy group having 1 to 4 carbon atoms; A phenyl group which may be substituted with an alkyl group of 4 to 4, an alkoxy group, a nitro group or an acetyl group; a heteroaromatic group having 3 to 5 carbon atoms; or a phenyl group which may be substituted with a chlorine atom or a fluorine atom.

Here, as the arylene group of R ¹¹⁰ , 1,2-phenylene group, 1,8-naphthylene group, etc., and as the alkylene group, methylene group, ethylene group, trimethylene group, tetramethylene group, phenylethylene group, norbornane Examples of the alkenylene group such as -2,3-diyl group include 1,2-vinylene group, 1-phenyl-1,2-vinylene group, 5-norbornene-2,3-diyl group and the like. The alkyl group for R ¹¹¹ is the same as R ^{101a to} R ^101c, and the alkenyl group is a vinyl group, 1-propenyl group, allyl group, 1-butenyl group, 3-butenyl group, isoprenyl group, 1- Pentenyl group, 3-pentenyl group, 4-pentenyl group, dimethylallyl group, 1-hexenyl group, 3-hexenyl group, 5-hexenyl group, 1-heptenyl group, 3-heptenyl group, 6-heptenyl group, 7-octenyl Groups such as alkoxyalkyl groups include methoxymethyl, ethoxymethyl, propoxymethyl, butoxymethyl, pentyloxymethyl, hexyloxymethyl, heptyloxymethyl, methoxyethyl, ethoxyethyl, Propoxyethyl, butoxyethyl, pentyloxyethyl, hexyloxyethyl, methoxypro Group, ethoxypropyl group, propoxypropyl group, butoxy propyl group, methoxybutyl group, ethoxybutyl group, propoxybutyl group, a methoxy pentyl group, an ethoxy pentyl group, a methoxy hexyl group, a methoxy heptyl group.

  In addition, examples of the optionally substituted alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group. As the alkoxy group of ˜4, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a tert-butoxy group and the like are an alkyl group having 1 to 4 carbon atoms, an alkoxy group, and a nitro group. As the phenyl group which may be substituted with an acetyl group, a phenyl group, a tolyl group, a p-tert-butoxyphenyl group, a p-acetylphenyl group, a p-nitrophenyl group, etc. are heterocycles having 3 to 5 carbon atoms. Examples of the aromatic group include a pyridyl group and a furyl group.

  Specific examples of the acid generator include onium salts such as diphenyliodonium trifluoromethanesulfonate, trifluoromethanesulfonate (p-tert-butoxyphenyl) phenyliodonium, diphenyliodonium p-toluenesulfonate, and p-toluenesulfone. Acid (p-tert-butoxyphenyl) phenyliodonium, triphenylsulfonium trifluoromethanesulfonate, trifluoromethanesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, bis (p-tert-butoxyphenyl) phenylsulfonium trifluoromethanesulfonate , Tris (p-tert-butoxyphenyl) sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate p-toluenesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, p-toluenesulfonic acid bis (p-tert-butoxyphenyl) phenylsulfonium, p-toluenesulfonic acid tris (p-tert-butoxyphenyl) sulfonium, nona Triphenylsulfonium fluorobutanesulfonate, triphenylsulfonium butanesulfonate, trimethylsulfonium trifluoromethanesulfonate, trimethylsulfonium p-toluenesulfonate, cyclohexylmethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, cyclohexyl p-toluenesulfonate Methyl (2-oxocyclohexyl) sulfonium, dimethylphenylsulfonium trifluoromethanesulfonate, -Toluenesulfonic acid dimethylphenylsulfonium, trifluoromethanesulfonic acid dicyclohexylphenylsulfonium, p-toluenesulfonic acid dicyclohexylphenylsulfonium, trifluoromethanesulfonic acid trinaphthylsulfonium, trifluoromethanesulfonic acid (2-norbornyl) methyl (2-oxocyclohexyl) sulfonium And onium salts such as ethylenebis [methyl (2-oxocyclopentyl) sulfonium trifluoromethanesulfonate] and 1,2′-naphthylcarbonylmethyltetrahydrothiophenium triflate.

  Diazomethane derivatives include bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (xylenesulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (cyclopentylsulfonyl) diazomethane, bis (n-butylsulfonyl) diazomethane Bis (isobutylsulfonyl) diazomethane, bis (sec-butylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, bis (n-amylsulfonyl) diazomethane Bis (isoamylsulfonyl) diazomethane, bis (sec-amylsulfonyl) diazomethane, bis (tert-amylsulfur) Nyl) diazomethane, 1-cyclohexylsulfonyl-1- (tert-butylsulfonyl) diazomethane, 1-cyclohexylsulfonyl-1- (tert-amylsulfonyl) diazomethane, 1-tert-amylsulfonyl-1- (tert-butylsulfonyl) diazomethane And the like.

  Examples of glyoxime derivatives include bis-O- (p-toluenesulfonyl) -α-dimethylglyoxime, bis-O- (p-toluenesulfonyl) -α-diphenylglyoxime, bis-O- (p-toluenesulfonyl)- α-dicyclohexylglyoxime, bis-O- (p-toluenesulfonyl) -2,3-pentanedione glyoxime, bis-O- (p-toluenesulfonyl) -2-methyl-3,4-pentanedione glyoxime, Bis-O- (n-butanesulfonyl) -α-dimethylglyoxime, bis-O- (n-butanesulfonyl) -α-diphenylglyoxime, bis-O- (n-butanesulfonyl) -α-dicyclohexylglyoxime Bis-O- (n-butanesulfonyl) -2,3-pentanedione glyoxime, bis-O- ( -Butanesulfonyl) -2-methyl-3,4-pentanedione glyoxime, bis-O- (methanesulfonyl) -α-dimethylglyoxime, bis-O- (trifluoromethanesulfonyl) -α-dimethylglyoxime, bis -O- (1,1,1-trifluoroethanesulfonyl) -α-dimethylglyoxime, bis-O- (tert-butanesulfonyl) -α-dimethylglyoxime, bis-O- (perfluorooctanesulfonyl)- α-dimethylglyoxime, bis-O- (cyclohexanesulfonyl) -α-dimethylglyoxime, bis-O- (benzenesulfonyl) -α-dimethylglyoxime, bis-O- (p-fluorobenzenesulfonyl) -α- Dimethylglyoxime, bis-O- (p-tert-butylbenzenesulfonyl) α- dimethylglyoxime, bis -O- (xylene sulfonyl)-.alpha.-dimethylglyoxime, and bis -O- (camphorsulfonyl)-.alpha.-glyoxime derivatives such as dimethylglyoxime.

  Examples of bissulfone derivatives include bisnaphthylsulfonylmethane, bistrifluoromethylsulfonylmethane, bismethylsulfonylmethane, bisethylsulfonylmethane, bispropylsulfonylmethane, bisisopropylsulfonylmethane, bis-p-toluenesulfonylmethane, and bisbenzenesulfonylmethane. Bissulfone derivatives can be mentioned.

Examples of β-ketosulfone derivatives include β-ketosulfone derivatives such as 2-cyclohexylcarbonyl-2- (p-toluenesulfonyl) propane and 2-isopropylcarbonyl-2- (p-toluenesulfonyl) propane.
Examples of the disulfone derivative include disulfone derivatives such as diphenyl disulfone derivatives and dicyclohexyl disulfone derivatives.

  Examples of the nitrobenzyl sulfonate derivative include nitrobenzyl sulfonate derivatives such as 2,6-dinitrobenzyl p-toluenesulfonate and 2,4-dinitrobenzyl p-toluenesulfonate.

  Examples of sulfonic acid ester derivatives include 1,2,3-tris (methanesulfonyloxy) benzene, 1,2,3-tris (trifluoromethanesulfonyloxy) benzene, 1,2,3-tris (p-toluenesulfonyloxy). Mention may be made of sulfonic acid ester derivatives such as benzene.

  Examples of sulfonic acid ester derivatives of N-hydroxyimide compounds include N-hydroxysuccinimide methanesulfonic acid ester, N-hydroxysuccinimide trifluoromethanesulfonic acid ester, N-hydroxysuccinimide ethanesulfonic acid ester, N-hydroxysuccinimide 1-propanesulfonic acid. Ester, N-hydroxysuccinimide 2-propanesulfonic acid ester, N-hydroxysuccinimide 1-pentanesulfonic acid ester, N-hydroxysuccinimide 1-octanesulfonic acid ester, N-hydroxysuccinimide p-toluenesulfonic acid ester, N-hydroxysuccinimide p-methoxybenzenesulfonic acid ester, N-hydroxysuccinimide 2-chloroethanesulfonic acid ester N-hydroxysuccinimide benzenesulfonic acid ester, N-hydroxysuccinimide-2,4,6-trimethylbenzenesulfonic acid ester, N-hydroxysuccinimide 1-naphthalenesulfonic acid ester, N-hydroxysuccinimide 2-naphthalenesulfonic acid ester, N- Hydroxy-2-phenylsuccinimide methanesulfonate, N-hydroxymaleimide methanesulfonate, N-hydroxymaleimide ethanesulfonate, N-hydroxy-2-phenylmaleimide methanesulfonate, N-hydroxyglutarimide methanesulfonate Ester, N-hydroxyglutarimide benzenesulfonic acid ester, N-hydroxyphthalimide methanesulfonic acid ester, N-hydro Siphthalimidobenzenesulfonic acid ester, N-hydroxyphthalimide trifluoromethanesulfonic acid ester, N-hydroxyphthalimide p-toluenesulfonic acid ester, N-hydroxynaphthalimide methanesulfonic acid ester, N-hydroxynaphthalimide benzenesulfonic acid ester, N- Hydroxy-5-norbornene-2,3-dicarboximide methanesulfonate, N-hydroxy-5-norbornene-2,3-dicarboximide trifluoromethanesulfonate, N-hydroxy-5-norbornene-2,3 -Sulphonic acid ester derivatives of N-hydroxyimide compounds such as dicarboximide p-toluenesulfonic acid ester.

In particular, triphenylsulfonium trifluoromethanesulfonate, trifluoromethanesulfonate (p-tert-butoxyphenyl) diphenylsulfonium, tris (p-tert-butoxyphenyl) sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, p -Toluenesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, p-toluenesulfonic acid tris (p-tert-butoxyphenyl) sulfonium, trifluoromethanesulfonic acid trinaphthylsulfonium, trifluoromethanesulfonic acid cyclohexylmethyl (2-oxocyclohexyl) ) Sulfonium, (2-norbornyl) methyl (2-oxocyclohexyl) sulfonyl trifluoromethanesulfonate , 1,2'-naphthyl carbonyl methyl tetrahydrothiophenium triflate onium salts such as,
Bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (n-butylsulfonyl) diazomethane, bis (isobutylsulfonyl) diazomethane, bis (sec-butylsulfonyl) diazomethane, bis ( diazomethane derivatives such as n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane,
Glyoxime derivatives such as bis-O- (p-toluenesulfonyl) -α-dimethylglyoxime, bis-O- (n-butanesulfonyl) -α-dimethylglyoxime,
Bissulfone derivatives such as bisnaphthylsulfonylmethane,
N-hydroxysuccinimide methanesulfonic acid ester, N-hydroxysuccinimide trifluoromethanesulfonic acid ester, N-hydroxysuccinimide 1-propanesulfonic acid ester, N-hydroxysuccinimide 2-propanesulfonic acid ester, N-hydroxysuccinimide 1-pentanesulfonic acid Preferred examples include sulfonate derivatives of N-hydroxyimide compounds such as esters, N-hydroxysuccinimide p-toluenesulfonate, N-hydroxynaphthalimide methanesulfonate, and N-hydroxynaphthalimide benzenesulfonate.

  In addition, the said acid generator can be used individually by 1 type or in combination of 2 or more types. Since onium salts are excellent in rectangularity improving effect and diazomethane derivatives and glyoxime derivatives are excellent in standing wave reducing effect, it is possible to finely adjust the profile by combining both.

  The addition amount of the acid generator is preferably 0.1 to 50 parts, more preferably 0.5 to 40 parts, with respect to 100 parts (parts by mass) of the base resin. If the amount is less than 0.1 part, the amount of acid generated during exposure is small and the sensitivity and resolution may be inferior. If the amount exceeds 50 parts, the transmittance of the resist may be lowered and the resolution may be inferior.

Further, the resist material of the present invention can be blended with a basic compound for improving storage stability.
As the basic compound, a compound that serves as a quencher for the acid to prevent the acid generated in a trace amount from the acid generator from causing the crosslinking reaction to proceed is suitable.
By adding a basic compound, the acid diffusion rate in the resist film is suppressed and resolution is improved, sensitivity change after exposure is suppressed, and substrate and environment dependency is reduced, and exposure margin and pattern profile are reduced. Etc. can be improved.

  Examples of such basic compounds include primary, secondary, and tertiary aliphatic amines, hybrid amines, aromatic amines, heterocyclic amines, nitrogen-containing compounds having a carboxy group, and sulfonyl groups. A nitrogen-containing compound having a hydroxyl group, a nitrogen-containing compound having a hydroxyl group, a nitrogen-containing compound having a hydroxyphenyl group, an alcoholic nitrogen-containing compound, an amide derivative, an imide derivative, and the like.

  Specifically, primary aliphatic amines include ammonia, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, pentylamine, tert- Amylamine, cyclopentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, cetylamine, methylenediamine, ethylenediamine, tetraethylenepentamine, etc. are exemplified as secondary aliphatic amines. Dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine, dipentylamine, disi Lopentylamine, dihexylamine, dicyclohexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, didodecylamine, dicetylamine, N, N-dimethylmethylenediamine, N, N-dimethylethylenediamine, N, N-dimethyltetraethylenepenta Examples of tertiary aliphatic amines include trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, and tripentylamine. , Tricyclopentylamine, trihexylamine, tricyclohexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, tridodecylamine, Examples include cetylamine, N, N, N ′, N′-tetramethylmethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethyltetraethylenepentamine and the like. Is done.

  Examples of hybrid amines include dimethylethylamine, methylethylpropylamine, benzylamine, phenethylamine, and benzyldimethylamine.

  Specific examples of aromatic amines and heterocyclic amines include aniline derivatives (eg, aniline, N-methylaniline, N-ethylaniline, N-propylaniline, N, N-dimethylaniline, 2-methylaniline, 3- Methylaniline, 4-methylaniline, ethylaniline, propylaniline, trimethylaniline, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2,4-dinitroaniline, 2,6-dinitroaniline, 3,5- Dinitroaniline, N, N-dimethyltoluidine, etc.), diphenyl (p-tolyl) amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, pyrrole derivatives (eg pyrrole, 2H-pyrrole, 1-methylpyrrole, 2,4-dim Lupyrrole, 2,5-dimethylpyrrole, N-methylpyrrole, etc.), oxazole derivatives (eg oxazole, isoxazole etc.), thiazole derivatives (eg thiazole, isothiazole etc.), imidazole derivatives (eg imidazole, 4-methylimidazole, 4 -Methyl-2-phenylimidazole, etc.), pyrazole derivatives, furazane derivatives, pyrroline derivatives (eg pyrroline, 2-methyl-1-pyrroline etc.), pyrrolidine derivatives (eg pyrrolidine, N-methylpyrrolidine, pyrrolidinone, N-methylpyrrolidone etc.) ), Imidazoline derivatives, imidazolidine derivatives, pyridine derivatives (eg pyridine, methylpyridine, ethylpyridine, propylpyridine, butylpyridine, 4- (1-butylpentyl) pyridine, dimethyl) Lysine, trimethylpyridine, triethylpyridine, phenylpyridine, 3-methyl-2-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 1-methyl-2-pyridone, 4-pyrrolidinopyridine, 1-methyl-4-phenylpyridine, 2- (1-ethylpropyl) pyridine, aminopyridine, dimethylaminopyridine, etc.), pyridazine derivatives, pyrimidine derivatives, pyrazine derivatives, pyrazoline derivatives, pyrazolidine derivatives, piperidine Derivatives, piperazine derivatives, morpholine derivatives, indole derivatives, isoindole derivatives, 1H-indazole derivatives, indoline derivatives, quinoline derivatives (eg quinoline, 3-quinoline carbo Nitriles), isoquinoline derivatives, cinnoline derivatives, quinazoline derivatives, quinoxaline derivatives, phthalazine derivatives, purine derivatives, pteridine derivatives, carbazole derivatives, phenanthridine derivatives, acridine derivatives, phenazine derivatives, 1,10-phenanthroline derivatives, adenine derivatives, adenosine Examples include derivatives, guanine derivatives, guanosine derivatives, uracil derivatives, uridine derivatives and the like.

  Furthermore, examples of the nitrogen-containing compound having a carboxy group include aminobenzoic acid, indolecarboxylic acid, amino acid derivatives (for example, nicotinic acid, alanine, arginine, aspartic acid, glutamic acid, glycine, histidine, isoleucine, glycylleucine, leucine, methionine. , Phenylalanine, threonine, lysine, 3-aminopyrazine-2-carboxylic acid, methoxyalanine) and the like, and examples of the nitrogen-containing compound having a sulfonyl group include 3-pyridinesulfonic acid, pyridinium p-toluenesulfonate, and the like. Nitrogen-containing compounds having a hydroxyl group, nitrogen-containing compounds having a hydroxyphenyl group, and alcoholic nitrogen-containing compounds include 2-hydroxypyridine, aminocresol, 2,4-quinolinediol, and 3-indolemethanol. Drate, monoethanolamine, diethanolamine, triethanolamine, N-ethyldiethanolamine, N, N-diethylethanolamine, triisopropanolamine, 2,2'-iminodiethanol, 2-aminoethanol, 3-amino-1-propanol 4-amino-1-butanol, 4- (2-hydroxyethyl) morpholine, 2- (2-hydroxyethyl) pyridine, 1- (2-hydroxyethyl) piperazine, 1- [2- (2-hydroxyethoxy) Ethyl] piperazine, piperidineethanol, 1- (2-hydroxyethyl) pyrrolidine, 1- (2-hydroxyethyl) -2-pyrrolidinone, 3-piperidino-1,2-propanediol, 3-pyrrolidino-1,2-propane Diol, 8-hydroxyuroli , 3-cuincridinol, 3-tropanol, 1-methyl-2-pyrrolidineethanol, 1-aziridineethanol, N- (2-hydroxyethyl) phthalimide, N- (2-hydroxyethyl) isonicotinamide, etc. Illustrated.

  Examples of amide derivatives include formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide and the like.

  Examples of imide derivatives include phthalimide, succinimide, maleimide and the like.

Furthermore, 1 type, or 2 or more types chosen from the basic compound shown by the following general formula (B) -1 can also be added.
N (X) _n (Y) _3-n (B) -1
(In the above formula, n = 1, 2, 3. The side chain X may be the same or different and can be represented by the following general formulas (X) -1 to (X) -3. Side chain Y Represents the same or different hydrogen atom or a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms, and may contain an ether group or a hydroxyl group, and Xs are bonded to form a ring. You may do it.)

Here, R ³⁰⁰ , R ³⁰² , and R ³⁰⁵ are linear or branched alkylene groups having 1 to 4 carbon atoms, and R ³⁰¹ and R ³⁰⁴ are hydrogen atoms, linear or branched structures having 1 to 20 carbon atoms. And a cyclic alkyl group, which may contain one or a plurality of hydroxy groups, ether groups, ester groups, and lactone rings.
R ³⁰³ is a single bond, a linear or branched alkylene group having 1 to 4 carbon atoms, R ³⁰⁶ is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a hydroxy group, One or a plurality of ether, ester groups and lactone rings may be contained.

Specific examples of the compound represented by formula (B) -1 are given below.
Tris (2-methoxymethoxyethyl) amine, tris {2- (2-methoxyethoxy) ethyl} amine, tris {2- (2-methoxyethoxymethoxy) ethyl} amine, tris {2- (1-methoxyethoxy) ethyl } Amine, Tris {2- (1-ethoxyethoxy) ethyl} amine, Tris {2- (1-ethoxypropoxy) ethyl} amine, Tris [2- {2- (2-hydroxyethoxy) ethoxy} ethyl] amine, 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo [8.8.8] hexacosane, 4,7,13,18-tetraoxa-1,10-diazabicyclo [8.5.5] Eicosane, 1,4,10,13-tetraoxa-7,16-diazabicyclooctadecane, 1-aza-12-crown-4 1-aza-15-crown-5, 1-aza-18-crown-6, tris (2-formyloxyethyl) amine, tris (2-formyloxyethyl) amine, tris (2-acetoxyethyl) amine, Tris (2-propionyloxyethyl) amine, tris (2-butyryloxyethyl) amine, tris (2-isobutyryloxyethyl) amine, tris (2-valeryloxyethyl) amine, tris (2-pivalo) Yloxyethyl) amine, N, N-bis (2-acetoxyethyl) 2- (acetoxyacetoxy) ethylamine, tris (2-methoxycarbonyloxyethyl) amine, tris (2-tert-butoxycarbonyloxyethyl) amine, tris [2- (2-Oxopropoxy) ethyl] amine, tris [2- (mes Xycarbonylmethyl) oxyethyl] amine, tris [2- (tert-butoxycarbonylmethyloxy) ethyl] amine, tris [2- (cyclohexyloxycarbonylmethyloxy) ethyl] amine, tris (2-methoxycarbonylethyl) amine, tris (2-ethoxycarbonylethyl) amine, N, N-bis (2-hydroxyethyl) 2- (methoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (methoxycarbonyl) ethylamine, N, N -Bis (2-hydroxyethyl) 2- (ethoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (ethoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2- (2 -Methoxyethoxycarbonyl) ethyl Amine, N, N-bis (2-acetoxyethyl) 2- (2-methoxyethoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2- (2-hydroxyethoxycarbonyl) ethylamine, N, N- Bis (2-acetoxyethyl) 2- (2-acetoxyethoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2-[(methoxycarbonyl) methoxycarbonyl] ethylamine, N, N-bis (2-acetoxy) Ethyl) 2-[(methoxycarbonyl) methoxycarbonyl] ethylamine, N, N-bis (2-hydroxyethyl) 2- (2-oxopropoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- ( 2-oxopropoxycarbonyl) ethylamine, N, N-bis (2- Droxyethyl) 2- (tetrahydrofurfuryloxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (tetrahydrofurfuryloxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2-[( 2-oxotetrahydrofuran-3-yl) oxycarbonyl] ethylamine, N, N-bis (2-acetoxyethyl) 2-[(2-oxotetrahydrofuran-3-yl) oxycarbonyl] ethylamine, N, N-bis (2 -Hydroxyethyl) 2- (4-hydroxybutoxycarbonyl) ethylamine, N, N-bis (2-formyloxyethyl) 2- (4-formyloxybutoxycarbonyl) ethylamine, N, N-bis (2-formyloxyethyl) ) 2- (2-Formyloxyethoxy) Rubonyl) ethylamine, N, N-bis (2-methoxyethyl) 2- (methoxycarbonyl) ethylamine, N- (2-hydroxyethyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (2-acetoxyethyl) ) Bis [2- (methoxycarbonyl) ethyl] amine, N- (2-hydroxyethyl) bis [2- (ethoxycarbonyl) ethyl] amine, N- (2-acetoxyethyl) bis [2- (ethoxycarbonyl) ethyl ], N- (3-hydroxy-1-propyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (3-acetoxy-1-propyl) bis [2- (methoxycarbonyl) ethyl] amine, N -(2-methoxyethyl) bis [2- (methoxycarbonyl) ethyl] amine, N-butylbis [2- ( Methoxycarbonyl) ethyl] amine, N-butylbis [2- (2-methoxyethoxycarbonyl) ethyl] amine, N-methylbis (2-acetoxyethyl) amine, N-ethylbis (2-acetoxyethyl) amine, N-methylbis ( 2-pivaloyloxyethyl) amine, N-ethylbis [2- (methoxycarbonyloxy) ethyl] amine, N-ethylbis [2- (tert-butoxycarbonyloxy) ethyl] amine, tris (methoxycarbonylmethyl) amine, Examples include, but are not limited to, tris (ethoxycarbonylmethyl) amine, N-butylbis (methoxycarbonylmethyl) amine, N-hexylbis (methoxycarbonylmethyl) amine, β- (diethylamino) -δ-valerolactone, and the like.

  Furthermore, 1 type, or 2 or more types of the basic compound which has the cyclic structure shown by the following general formula (B) -2 can also be added.

（式中、Ｘは前述の通り、Ｒ^３０７は炭素数２〜２０の直鎖状、分岐状のアルキレン基であり、カルボニル基、エーテル基、エステル基、スルフィドを１個あるいは複数個含んでいても良い。）

(In the formula, as described above, R ³⁰⁷ is a linear or branched alkylene group having 2 to 20 carbon atoms and contains one or more carbonyl groups, ether groups, ester groups and sulfides. Is also good.)

  (B) -2 is specifically 1- [2- (methoxymethoxy) ethyl] pyrrolidine, 1- [2- (methoxymethoxy) ethyl] piperidine, 4- [2- (methoxymethoxy) ethyl] morpholine, 1- [2-[(2-methoxyethoxy) methoxy] ethyl] pyrrolidine, 1- [2-[(2-methoxyethoxy) methoxy] ethyl] piperidine, 4- [2-[(2-methoxyethoxy) methoxy] Ethyl] morpholine, 2- (1-pyrrolidinyl) ethyl acetate, 2-piperidinoethyl acetate, 2-morpholinoethyl acetate, 2- (1-pyrrolidinyl) ethyl formate, 2-piperidinoethyl propionate, 2-morpholinoethyl acetoxyacetate, methoxyacetic acid 2- (1-pyrrolidinyl) ethyl, 4- [2- (methoxycarbonyloxy) ethyl] morpholine 1- [2- (t-butoxycarbonyloxy) ethyl] piperidine, 4- [2- (2-methoxyethoxycarbonyloxy) ethyl] morpholine, methyl 3- (1-pyrrolidinyl) propionate, 3-piperidinopropion Acid methyl, methyl 3-morpholinopropionate, methyl 3- (thiomorpholino) propionate, methyl 2-methyl-3- (1-pyrrolidinyl) propionate, ethyl 3-morpholinopropionate, methoxy 3-piperidinopropionate Carbonylmethyl, 2-hydroxyethyl 3- (1-pyrrolidinyl) propionate, 2-acetoxyethyl 3-morpholinopropionate, 2-oxotetrahydrofuran-3-yl 3- (1-pyrrolidinyl) propionate, 3-morpholinopropionic acid Tetrahydrofurfuryl, 3- Glycidyl peridinopropionate, 2-methoxyethyl 3-morpholinopropionate, 2- (2-methoxyethoxy) ethyl 3- (1-pyrrolidinyl) propionate, butyl 3-morpholinopropionate, cyclohexyl 3-piperidinopropionate , Α- (1-pyrrolidinyl) methyl-γ-butyrolactone, β-piperidino-γ-butyrolactone, β-morpholino-δ-valerolactone, methyl 1-pyrrolidinyl acetate, methyl piperidinoacetate, methyl morpholinoacetate, methyl thiomorpholinoacetate, Examples include ethyl 1-pyrrolidinyl acetate and 2-methoxyethyl morpholinoacetate.

  Furthermore, a basic compound containing a cyano group represented by general formulas (B) -3 to (B) -6 can be added.

（式中、Ｘ、Ｒ^３０７、ｎは前述の通り、Ｒ^３０８、Ｒ^３０９は同一又は異種の炭素数１〜４の直鎖状、分岐状のアルキレン基である。）

(In the formula, X, R ³⁰⁷ and n are as described above, and R ³⁰⁸ and R ³⁰⁹ are the same or different linear or branched alkylene groups having 1 to 4 carbon atoms.)

  Specific examples of the base containing a cyano group include 3- (diethylamino) propiononitrile, N, N-bis (2-hydroxyethyl) -3-aminopropiononitrile, and N, N-bis (2-acetoxyethyl). -3-aminopropiononitrile, N, N-bis (2-formyloxyethyl) -3-aminopropiononitrile, N, N-bis (2-methoxyethyl) -3-aminopropiononitrile, N, N -Bis [2- (methoxymethoxy) ethyl] -3-aminopropiononitrile, methyl N- (2-cyanoethyl) -N- (2-methoxyethyl) -3-aminopropionate, N- (2-cyanoethyl) -N- (2-hydroxyethyl) -3-aminopropionic acid methyl, N- (2-acetoxyethyl) -N- (2-cyanoethyl) -3-aminopro Methyl onate, N- (2-cyanoethyl) -N-ethyl-3-aminopropiononitrile, N- (2-cyanoethyl) -N- (2-hydroxyethyl) -3-aminopropiononitrile, N- ( 2-acetoxyethyl) -N- (2-cyanoethyl) -3-aminopropiononitrile, N- (2-cyanoethyl) -N- (2-formyloxyethyl) -3-aminopropiononitrile, N- (2 -Cyanoethyl) -N- (2-methoxyethyl) -3-aminopropiononitrile, N- (2-cyanoethyl) -N- [2- (methoxymethoxy) ethyl] -3-aminopropiononitrile, N- ( 2-cyanoethyl) -N- (3-hydroxy-1-propyl) -3-aminopropiononitrile, N- (3-acetoxy-1-propyl) -N- (2 Cyanoethyl) -3-aminopropiononitrile, N- (2-cyanoethyl) -N- (3-formyloxy-1-propyl) -3-aminopropiononitrile, N- (2-cyanoethyl) -N-tetrahydrofur Furyl-3-aminopropiononitrile, N, N-bis (2-cyanoethyl) -3-aminopropiononitrile, diethylaminoacetonitrile, N, N-bis (2-hydroxyethyl) aminoacetonitrile, N, N-bis ( 2-acetoxyethyl) aminoacetonitrile, N, N-bis (2-formyloxyethyl) aminoacetonitrile, N, N-bis (2-methoxyethyl) aminoacetonitrile, N, N-bis [2- (methoxymethoxy) ethyl Aminoacetonitrile, N-cyanomethyl-N- (2-methoxyethyl) ) Methyl 3-aminopropionate, methyl N-cyanomethyl-N- (2-hydroxyethyl) -3-aminopropionate, methyl N- (2-acetoxyethyl) -N-cyanomethyl-3-aminopropionate, N -Cyanomethyl-N- (2-hydroxyethyl) aminoacetonitrile, N- (2-acetoxyethyl) -N- (cyanomethyl) aminoacetonitrile, N-cyanomethyl-N- (2-formyloxyethyl) aminoacetonitrile, N-cyanomethyl -N- (2-methoxyethyl) aminoacetonitrile, N-cyanomethyl-N- [2- (methoxymethoxy) ethyl] aminoacetonitrile, N- (cyanomethyl) -N- (3-hydroxy-1-propyl) aminoacetonitrile, N- (3-acetoxy-1-propyl) -N (Cyanomethyl) aminoacetonitrile, N-cyanomethyl-N- (3-formyloxy-1-propyl) aminoacetonitrile, N, N-bis (cyanomethyl) aminoacetonitrile, 1-pyrrolidinepropiononitrile, 1-piperidinepropiononitrile, 4-morpholinepropiononitrile, 1-pyrrolidineacetonitrile, 1-piperidineacetonitrile, 4-morpholineacetonitrile, cyanomethyl 3-diethylaminopropionate, cyanomethyl N, N-bis (2-hydroxyethyl) -3-aminopropionate, N, Cyanomethyl N-bis (2-acetoxyethyl) -3-aminopropionate, cyanomethyl N, N-bis (2-formyloxyethyl) -3-aminopropionate, N, N-bis (2-methoxyethyl) Cyanomethyl 3-aminopropionate, N, N-bis [2- (methoxymethoxy) ethyl] -3-aminopropionate cyanomethyl, 3-diethylaminopropionic acid (2-cyanoethyl), N, N-bis (2-hydroxyethyl) ) -3-Aminopropionic acid (2-cyanoethyl), N, N-bis (2-acetoxyethyl) -3-aminopropionic acid (2-cyanoethyl), N, N-bis (2-formyloxyethyl) -3 Aminopropionic acid (2-cyanoethyl), N, N-bis (2-methoxyethyl) -3-aminopropionic acid (2-cyanoethyl), N, N-bis [2- (methoxymethoxy) ethyl] -3- Aminopropionic acid (2-cyanoethyl), 1-pyrrolidinepropionate cyanomethyl, 1-piperidinepropionate cyano Examples include methyl, cyanomethyl 4-morpholine propionate, 1-pyrrolidinepropionic acid (2-cyanoethyl), 1-piperidinepropionic acid (2-cyanoethyl), 4-morpholine propionic acid (2-cyanoethyl), and the like.

  In addition, the compounding quantity of a basic compound is 0.001-2 parts with respect to 100 parts of all base resins, Especially 0.01-1 part is suitable. If the blending amount is less than 0.001 part, the blending effect is small, and if it exceeds 2 parts, the sensitivity may be too low.

  Specific examples of the crosslinking agent that can be used in the present invention include a melamine compound, a guanamine compound, a glycoluril compound, or a urea compound substituted with at least one group selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group. Examples of the compound include a double bond such as an epoxy compound, an isocyanate compound, an azide compound, and an alkenyl ether group. These may be used as additives, but may be introduced as pendant groups in the polymer side chain. A compound containing a hydroxy group can also be used as a crosslinking agent.

  Among specific examples of the crosslinking agent, when an epoxy compound is exemplified, tris (2,3-epoxypropyl) isocyanurate, trimethylolmethane triglycidyl ether, trimethylolpropane triglycidyl ether, triethylolethane triglycidyl ether and the like can be mentioned. It is done. Specific examples of the melamine compound include hexamethylol melamine, hexamethoxymethyl melamine, a compound in which 1 to 6 methylol groups of hexamethylol melamine are methoxymethylated, and a mixture thereof, hexamethoxyethyl melamine, hexaacyloxymethyl melamine, Examples include compounds in which 1 to 6 methylol groups of hexamethylolmelamine are acyloxymethylated, and mixtures thereof. Examples of the guanamine compound include tetramethylolguanamine, tetramethoxymethylguanamine, a compound in which 1 to 4 methylol groups of tetramethylolguanamine are methoxymethylated, and a mixture thereof, tetramethoxyethylguanamine, tetraacyloxyguanamine, and tetramethylolguanamine. Examples include compounds in which 4 methylol groups are acyloxymethylated, and mixtures thereof. Examples of the glycoluril compound include tetramethylol glycoluril, tetramethoxyglycoluril, tetramethoxymethylglycoluril, a compound in which 1 to 4 methylol groups of tetramethylolglycoluril are methoxymethylated, and a mixture thereof. Examples thereof include compounds in which 1 to 4 methylol groups are acyloxymethylated, and mixtures thereof. Examples of the urea compound include tetramethylol urea, tetramethoxymethyl urea, compounds in which 1 to 4 methylol groups of tetramethylol urea are methoxymethylated, a mixture thereof, and tetramethoxyethyl urea.

  Examples of the isocyanate compound include tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, and cyclohexane diisocyanate. Examples of the azide compound include 1,1′-biphenyl-4,4′-bisazide and 4,4′-methylidenebis. Examples include azide and 4,4′-oxybisazide.

  Examples of the compound containing an alkenyl ether group include ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,2-propanediol divinyl ether, 1,4-butanediol divinyl ether, tetramethylene glycol divinyl ether, neopentyl glycol divinyl ether, Examples include trimethylolpropane trivinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether, trimethylolpropane trivinyl ether, and the like.

  The blending amount of the crosslinking agent in the resist material of the present invention is preferably 5 to 50 parts, particularly preferably 10 to 40 parts, relative to 100 parts (parts by mass, the same applies hereinafter) of the base polymer (total resin).

In the resist material of the present invention, a surfactant can be further added for reasons such as improving coating properties.
Examples of surfactants include, but are not limited to, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene olein ether, Polyoxyethylene alkyl allyl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether, polyoxyethylene polyoxypropylene block copolymers, sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate and sorbitan monostearate Polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan mono Nonionic surfactants of polyoxyethylene sorbitan fatty acid esters such as stearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, F-top EF301, EF303, EF352 (Tochem Products), MegaFuck F171, F172 , F173 (Dainippon Ink and Chemicals), Florard FC430, FC431 (Sumitomo 3M), Asahi Guard AG710, Surflon S-381, S-382, SC101, SC102, SC103, SC104, SC105, SC106, Surfinol E1004, KH- Fluorosurfactants such as 10, KH-20, KH-30, KH-40 (Asahi Glass), organosiloxane polymers KP341, X-70-092, X-70-09 (Shin-Etsu Chemical), acrylic acid or methacrylic acid Polyflow No. 75, no. 95 (Kyoeisha Yushi Chemical Co., Ltd.), among which FC430, Surflon S-381, Surfynol E1004, KH-20, KH-30 are preferred. These can be used alone or in combination of two or more.

  As addition amount of surfactant in the resist material of this invention, 2 mass parts or less are preferable with respect to 100 mass parts of solid content in a resist material composition, and 1 mass part or less is more preferable.

  The present invention provides a resist material containing a polymer compound having a repeating unit represented by the general formulas (1) to (5) and an acid generator, a crosslinking agent, an organic solvent, a basic compound, etc. for various integrated circuit manufacture. When used, it is not particularly limited and can be applied to a known lithography technique.

For example, the resist material of the present invention is formed on a substrate (Si, SiO ₂ , SiN, SiON, TiN, WSi, BPSG, SOG, organic antireflection film, Cr, CrO, CrON, MoSi, etc.) for manufacturing integrated circuits. , Spin coating, roll coating, flow coating, dip coating, spray coating, doctor coating, and the like so that the coating film thickness is 0.1 to 2.0 μm, and 60 to 150 on a hot plate. Prebaking at 1 ° C. for 1 to 10 minutes, preferably 80 to 120 ° C. for 1 to 5 minutes.

Next, a light source selected from high energy rays such as ultraviolet rays, far ultraviolet rays, electron beams, X-rays, excimer lasers, γ rays, and synchrotron radiation, preferably an intended pattern at an exposure wavelength of 300 nm or less, through a predetermined mask or directly And exposure. Exposure, if light exposure 1 to 200 mJ / cm ^2, preferably about 10 to 100 mJ / cm ² or so, also, if the electron beam exposure, 0.1 to 20 / cm ^2, preferably about 3 It is preferable to perform exposure so as to be about 10 μC / cm ² . Post exposure baking (PEB) is performed on a hot plate at 60 to 150 ° C. for 1 to 5 minutes, preferably 80 to 120 ° C. for 1 to 3 minutes.

  Furthermore, 0.1-5%, preferably 2-3% tetramethylammonium hydroxide (TMAH) or other alkaline aqueous developer is used for 0.1-3 minutes, preferably 0.5-2 minutes. Development is performed by a conventional method such as a (dip) method, a paddle method, or a spray method. Thus, the exposed portion of the resist film is difficult to be dissolved by the developer because the base resin is cross-linked, and the unexposed resist is dissolved to form a target pattern on the substrate. In addition, the resist material of the present invention is a fine patterning by using 254 to 193 nm deep ultraviolet rays, 157 nm vacuum ultraviolet rays, electron beams, X-rays, soft X-rays, excimer lasers, γ rays, synchrotron radiation, among high energy rays. Ideal for.

EXAMPLES Hereinafter, although a synthesis example, a comparative synthesis example, an Example, and a comparative example are shown and this invention is demonstrated concretely, this invention is not limited by these description.
In addition, the following synthesis examples 1-4 and the following Examples 1-4 using the same are illustrated for reference.
(Synthesis Example 1)
To a 100 mL flask, 2.4 g of α-hydroxymethyl acrylic acid, 14.8 g of α-hydroxymethyl acrylic acid γ-butyrolactone, and 10 g of tetrahydrofuran as a solvent were added. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen flow were repeated three times. After raising the temperature to room temperature, 0.2 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. This reaction solution was precipitated in a 100 mL solution of isopropyl alcohol, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain 8.1 g of a white polymer (Polymer 1).

When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Copolymerization composition ratio α-hydroxymethyl acrylic acid: α-hydroxymethyl acrylic acid γ-butyrolactone = 0.2: 0.8
Mass average molecular weight (Mw) = 6,500
Molecular weight distribution (Mw / Mn) = 1.55
This polymer is referred to as polymer 1.

(Synthesis Example 2)
In a 100 mL flask, 2.6 g of α-hydroxymethyl acrylic acid, 18.9 g of α-hydroxymethyl acrylate-3-hydroxy-1-adamantyl, and 10 g of tetrahydrofuran as a solvent were added. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen flow were repeated three times. After raising the temperature to room temperature, 0.2 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. This reaction solution was precipitated in 100 mL of isopropyl alcohol, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain 15.8 g of a white polymer (Polymer 2).

When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Copolymerization composition ratio α-hydroxymethylacrylic acid: α-hydroxymethylacrylic acid-3-hydroxy-1-adamantyl = 0.25: 0.75
Mass average molecular weight (Mw) = 5,500
Molecular weight distribution (Mw / Mn) = 1.52
This polymer is designated as Polymer 2.

(Synthesis Example 3)
In a 100 mL flask, α-hydroxymethylacrylic acid 2.5 g, α-hydroxymethylacrylic acid-5-oxo-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-2-yl 19.0 g, solvent As a result, 10 g of tetrahydrofuran was added. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen flow were repeated three times. After raising the temperature to room temperature, 0.2 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. This reaction solution was precipitated in a 100 mL solution of isopropyl alcohol, and the obtained white solid was filtered and dried under reduced pressure at 60 ° C. to obtain 14.6 g of a white polymer (Polymer 3).

When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Copolymerization composition ratio α-hydroxymethylacrylic acid: α-hydroxymethylacrylic acid-5-oxo-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-2-yl = 0.2: 0.8
Mass average molecular weight (Mw) = 4,700
Molecular weight distribution (Mw / Mn) = 1.45
This polymer is designated as Polymer 3.

(Synthesis Example 4)
In a 100-mL flask, 2.6 g of α-hydroxymethylacrylic acid and α-hydroxymethylacrylic acid-4-oxatricyclo [4.3.1.1. ^3,8 ] 18.8 g of undecan-5-one and 10 g of tetrahydrofuran as a solvent were added. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen flow were repeated three times. After raising the temperature to room temperature, 0.2 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. This reaction solution was precipitated in a 100 mL solution of isopropyl alcohol, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain 17.1 g of a white polymer (Polymer 4).

When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Copolymerization composition ratio α-hydroxymethylacrylic acid: α-hydroxymethylacrylic acid-4-oxatricyclo [4.3.1.1. ^3,8 ] undecan-5-one = 0.25: 0.75
Mass average molecular weight (Mw) = 3,900
Molecular weight distribution (Mw / Mn) = 1.41
This polymer is designated as polymer 4.

(Synthesis Example 5)
In a 100 mL flask, 2.6 g of α-hydroxymethylacrylic acid, 14.2 g of α-hydroxymethylacrylic acid-5-oxo-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-2-yl, methacryl 9.4 g of acid 5,6- [3,3,3-trifluoro-2-hydroxy-2-trifluoroethylpropyl] bicyclo [2.2.1] hept-2-yl and 10 g of tetrahydrofuran as a solvent were added. . The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen flow were repeated three times. After raising the temperature to room temperature, 0.2 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. This reaction solution was precipitated in 100 mL of isopropyl alcohol, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain 19.4 g of a white polymer (Polymer 5).

When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Copolymerization composition ratio αhydroxymethylacrylic acid: αhydroxymethylacrylic acid-5-oxo-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-2-yl: methacrylic acid 5,6- [ 3,3,3-trifluoro-2-hydroxy-2-trifluoroethylpropyl] bicyclo [2.2.1] hept-2-yl = 0.2: 0.6: 0.2
Mass average molecular weight (Mw) = 4,900
Molecular weight distribution (Mw / Mn) = 1.61
This polymer is designated as polymer 5.

(Synthesis Example 6)
In a 100-mL flask, 1.8 g of α-hydroxymethylacrylic acid, 16.2 g of α-hydroxymethylacrylic acid-5-oxo-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-2-yl, α 15.4 g of hydroxymethylacrylic acid-3,5-di (2-hydroxy-1,1,1,3,3,3-hexafluoro-2-propyl) cyclohexyl and 10 g of tetrahydrofuran as a solvent were added. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen flow were repeated three times. After raising the temperature to room temperature, 0.2 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. This reaction solution was precipitated in 100 mL of isopropyl alcohol, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain 22.4 g of a white polymer (polymer 6).

When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Copolymerization composition ratio α-hydroxymethylacrylic acid: α-hydroxymethylacrylic acid-5-oxo-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-2-yl: α-hydroxymethylacrylic acid-3 , 5-Di (2-hydroxy-1,1,1,3,3,3-hexafluoro-2-propyl) cyclohexyl = 0.15: 0.65: 0.2
Mass average molecular weight (Mw) = 4,800
Molecular weight distribution (Mw / Mn) = 1.54
This polymer is designated as polymer 6.

(Synthesis Example 7)
In a 100 mL flask, 2.4 g of α-hydroxymethylacrylic acid, 16.2 g of α-hydroxymethylacrylic acid-5-oxo-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-2-yl, methacryl 10.4 g of acid 5-hydroxy-5-trifluoromethyl-6,6-difluoro-bicyclo [2.2.1] hept-2-yl and 10 g of tetrahydrofuran as a solvent were added. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen flow were repeated three times. After raising the temperature to room temperature, 0.2 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. This reaction solution was precipitated in 100 mL of isopropyl alcohol, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain 22.4 g of a white polymer (Polymer 7).

When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Copolymerization composition ratio α-hydroxymethyl acrylic acid: α-hydroxymethyl acrylic acid-5-oxo-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-2-yl: 5-hydroxy-5 methacrylate -Trifluoromethyl-6,6-difluoro-bicyclo [2.2.1] hept-2-yl = 0.2: 0.6: 0.2
Mass average molecular weight (Mw) = 4,300
Molecular weight distribution (Mw / Mn) = 1.44
This polymer is designated as polymer 7.

(Synthesis Example 8)
In a 100 mL flask, 4.8 g of α-hydroxymethylacrylic acid-4-carboxycyclohexyl and 5-hydroxy-4-acrylic acid-4-oxotrioxa [4.2.1.0 ^3,7 ] nonan-2-yl 16.2 g, 10.4 g of 5-hydroxy-5-trifluoromethyl-6,6-difluoro-bicyclo [2.2.1] hept-2-yl methacrylate, and 10 g of tetrahydrofuran as a solvent were added. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen flow were repeated three times. After raising the temperature to room temperature, 0.2 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. This reaction solution was precipitated in a 100 mL solution of isopropyl alcohol, and the obtained white solid was filtered and dried under reduced pressure at 60 ° C. to obtain 22.4 g of a white polymer (polymer 8).

When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Copolymerization composition ratio α-hydroxymethylacrylic acid-4-carboxycyclohexyl: α-hydroxymethylacrylic acid-5-oxo-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-2-yl: methacrylic acid 5-hydroxy-5-trifluoromethyl-6,6-difluoro-bicyclo [2.2.1] hept-2-yl = 0.25: 0.5: 0.25
Mass average molecular weight (Mw) = 6,300
Molecular weight distribution (Mw / Mn) = 1.61
This polymer is designated as polymer 8.

(Comparative Synthesis Example 1)
To a 100 mL flask was added 3.4 g of methacrylic acid, 10.3 g of 2-hydroxyethyl methacrylate, 17.1 g of γ-butyrolactone methacrylate, and 10 g of tetrahydrofuran as a solvent. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen flow were repeated three times. After raising the temperature to room temperature, 0.2 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. This reaction solution was precipitated in 100 mL of isopropyl alcohol, and the obtained white solid was filtered and dried under reduced pressure at 60 ° C. to obtain 16.9 g of a white polymer (Comparative Polymer 1).

When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Copolymerization composition ratio Methacrylic acid: methacrylic acid-2-hydroxyethyl: methacrylic acid γ-butyrolactone = 20: 40: 40
Mass average molecular weight (Mw) = 13000
Molecular weight distribution (Mw / Mn) = 1.88
This polymer is referred to as comparative polymer 1.

(Examples and comparative examples)
[Preparation of resist material]
Polymers shown in Synthesis Examples 1 to 8, Polymers shown in Comparative Synthesis Example 1, acid generators shown in the following PAG1, PAG2, tributylamine / triethanolamine, and TMMEA / AAA / AACN shown below A basic compound and a crosslinking agent represented by the following TMGU were dissolved in an organic solvent at a ratio shown in Table 1 and filtered through a 0.2 μm size filter to prepare resist solution solutions.

塩基性化合物： ＴＭＭＥＡ、ＡＡＡ、ＡＡＣＮ（下記構造式参照）

架橋剤： ＴＭＧＵ（下記構造式参照）

有機溶剤： ＰＧＭＥＡ（プロピレングリコールモノメチルエーテルアセテート） Each composition in Table 1 is as follows.
Polymers 1-8: From Synthesis Examples 1-8 Comparative Polymer 1: From Comparative Synthesis Example 1 Acid generator: PAG1, PAG2 (see the following structural formula)

Basic compounds: TMMEA, AAA, AACN (see the structural formula below)

Crosslinking agent: TMGU (see the following structural formula)

Organic solvent: PGMEA (propylene glycol monomethyl ether acetate)

[Exposure patterning evaluation]
A solution of the resist material thus prepared (Examples 1 to 13 and Comparative Example 1) was spin-coated on an antireflection film obtained by depositing ARC-29A (Nissan Chemical Co., Ltd.) with a film thickness of 78 nm on a silicon wafer. Then, using a hot plate, the resist was baked at 130 ° C. for 90 seconds to make the resist thickness 300 nm.
Furthermore, exposure was performed using an ArF excimer laser stepper (Nikon Corporation, NSR-S305B, NA-0.68, σ0.85, 2/3 annular illumination, Cr mask), and immediately after exposure, baking was performed at 130 ° C. for 90 seconds. Development was performed with an aqueous solution of 2.38% tetramethylammonium hydroxide for 60 seconds to obtain a negative pattern (Examples 1 to 13, Comparative Example 1).

The obtained resist pattern was evaluated as follows, and the results are shown in Table 1.
The exposure amount for resolving 0.15 μm line and space at 1: 1 was defined as the resist sensitivity, and the minimum line width of the separated line and space at this exposure amount was defined as the resolution of the evaluation resist.

As shown in Table 1, the resist materials according to the present invention (Examples 5 to 13) have high crosslinking efficiency, reduce pattern collapse by suppressing swelling during development, and satisfy sufficient resolution and sensitivity. I understand. On the other hand, in the comparative example, it can be seen that both sensitivity and resolution are poor.
Further, as can be seen by comparing Examples 1 to 4 and Examples 5 to 8, the resist material having an acrylate having an alcohol substituted at the α-position with a fluoroalkyl group as an adhesive group as a repeating unit has a resolution. It can be seen that the sensitivity is better.

The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and any device that exhibits the same function and effect is the present invention. It is included in the technical scope of the invention.

Claims (8)

A negative resist material characterized in that it contains at least a polymer compound having a repeating unit represented by the following general formula (2).

(In the general formula (2), R ² and R ³ may be a hydrogen atom, or R ² and R ³ may be bonded to form a methylene group, an ethylene group, —O—, —S—, ⁴ is a single bond, an alkylene group having 1 to 4 carbon atoms, an alkylene group in which all or a part of hydrogen atoms are substituted with fluorine atoms, R ⁵ and R ⁶ are hydrogen atoms, fluorine atoms, alkyl having 1 to 4 carbon atoms A group, an alkyl group in which all or some of the hydrogen atoms are substituted with fluorine atoms, and at least one of R ⁵ and R ⁶ contains one or more fluorine atoms, and n is 1 or 2.) A negative resist material comprising at least a polymer compound having a repeating unit represented by the following general formula (3).

(In the general formula (3), R ² and R ³ may be a hydrogen atom, or R ² and R ³ may be bonded to form a methylene group, an ethylene group, —O—, —S—, ⁴ is a single bond, an alkylene group having 1 to 4 carbon atoms, an alkylene group in which all or a part of hydrogen atoms are substituted with fluorine atoms, R ⁵ and R ⁶ are hydrogen atoms, fluorine atoms, alkyl having 1 to 4 carbon atoms Group, an alkyl group in which all or some of the hydrogen atoms are substituted with fluorine atoms, and at least one of R ⁵ and R ⁶ contains one or more fluorine atoms, R ⁷ is a hydrogen atom, a methyl group, —CH ₂ —O—R ^1. R ¹ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a ring or a bridged ring, may contain a hetero atom, and is at least a carboxyl group. , Hydroxy group, lactone ring, ester group, ether group In .R ⁸ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a ring-bridged, which has the above, and may contain a hetero atom, at least a carboxyl group, hydroxy group, a lactone ring, (It has one or more of an ester group and an ether group. A and b are in the range of 0 <a <1, 0 <b <1, 0 <a + b ≦ 1, and n is 1 or 2.) A negative resist material characterized in that it contains at least a polymer compound having a repeating unit represented by the following general formula (4).

(In the general formula (4), R ¹ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a ring or a bridged ring, may contain a hetero atom, and is at least a carboxyl group, a hydroxy group Any one or more of a group, a lactone ring, an ester group, and an ether group, R ⁴ is a single bond, an alkylene group having 1 to 4 carbon atoms, or an alkylene group in which all or some of the hydrogen atoms are substituted with fluorine atoms. R ⁹ is a hydrogen atom or a methyl group, and R ¹⁰ is a linear, branched, cyclic or bridged hydrocarbon group having 1 to 12 carbon atoms, all or even if some of the hydrogen atoms are substituted with fluorine atoms may, hydroxy group, an ether group, a lactone ring, -O -, - which may have any one or more S- of .R ^11, R ¹² Are independently hydrogen atom, fluorine atom, charcoal C1-4 alkyl group, all or part of an alkyl group wherein a hydrogen atom has been substituted with a fluorine atom, including at least R ¹¹ and one or more fluorine atoms either one of R ^12. In addition, R Any one of ¹¹ and R ¹² may be connected to R ¹⁰ to form a ring, R ¹⁶ is a single bond or an alkylene group having 1 to 4 carbon atoms, and c and d are 0 <c <1. 0 <d <1, 0 <c + d ≦ 1, n is 1 or 2.) A negative resist material comprising at least a polymer compound having a repeating unit represented by the following general formula (5).

(In the above general formula (5), R ¹ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a ring or a bridged ring, may contain a hetero atom, and is at least a carboxyl group, a hydroxy group Any one or more of a group, a lactone ring, an ester group, and an ether group, R ⁴ is a single bond, an alkylene group having 1 to 4 carbon atoms, an alkylene group in which all or part of hydrogen atoms are substituted with fluorine atoms, R ⁵ and R ⁶ are a hydrogen atom, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an alkyl group in which all or part of the hydrogen atoms are substituted with fluorine atoms, and at least one of R ⁵ and R ⁶ And R ⁹ is a hydrogen atom or a methyl group, and D ¹ , E ¹ and F ¹ are each a cyclic hydrocarbon group or a bridged cyclic hydrocarbon group having 3 to 12 carbon atoms. Yes, hydroxy group, -O- R ¹³ , R ¹⁴ , and R ¹⁵ are each independently a hydrogen atom, a fluorine atom, or a trifluoromethyl group, and at least one of R ^{13 to} R ¹⁵ is 1 R ¹⁶ is a single bond or an alkylene group having 1 to 4 carbon atoms, R ¹⁷ is a hydrogen atom or a methyl group, c, d-1, d-2, d-3 are 0 <C <1, 0 ≦ (d−1) <1, 0 ≦ (d−2) <1, 0 ≦ (d−3) <1, 0 <(d−1) + (d−2) + ( d-3) <1 range, n is 1 or 2) A negative resist material described in any one of claims 1 to 4, a negative resist, which is a chemically amplified negative resist composition containing at least an organic solvent and an acid generator material. Negative resist material, characterized in that a negative resist material described is a chemically amplified negative resist composition further contains a crosslinking agent in claim 5. Negative resist material, characterized in that a negative resist material described is more chemically amplified negative resist composition basic compound is blended as an additive to claim 5 or claim 6. Using at least a step of applying the negative resist material according to any one of claims 1 to 7 on a substrate, a step of exposing to a high energy beam or an electron beam after heat treatment, and a developer. And a developing process.